C1,C2-Bridged Ligands and Catalysts

ABSTRACT

The present disclosure provides catalyst compounds including a nonsymmetric bridged amine bis(phenolate), catalyst systems including such, and uses thereof. Catalyst compounds, catalyst systems, and processes of the present disclosure can provide high comonomer content and high molecular weight polymers having narrow Mw/Mn values, contributing to good processability for the polymer itself and for the polymer used in a composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/737,391, filed Sep. 27, 2018, the disclosure of which is incorporatedherein by reference.

FIELD

The present disclosure provides ligand compounds and catalyst compoundsincluding a nonsymmetric bridged amine bis(phenolate) transition metalcomplexes, production, and uses thereof.

BACKGROUND

Olefin polymerization catalysts are of great use in industry andpolyolefins are widely used commercially because of their robustphysical properties. Hence, there is interest in finding new catalystsystems that increase the utility/efficiency of the catalyst andfacilitate the production of polymers having improved properties.

Low density polyethylene is generally prepared at high pressure usingfree radical initiators, or in gas phase processes using Ziegler-Nattaor vanadium catalysts. Suitable low density polyethylene has a densityin the range of 0.916 g/cm³ to 0.940 g/cm³. Suitable low densitypolyethylene produced using free radical initiators is known in theindustry as “LDPE”. LDPE is also known as “branched” or “heterogeneouslybranched” polyethylene because of the relatively large number of longchain branches extending from the main polymer backbone. Polyethylene inthe same density range, e.g., 0.916 g/cm³ to 0.940 g/cm³, which islinear and does not contain long chain branching, is known as “linearlow density polyethylene” (“LLDPE”) and can be produced by conventionalZiegler-Natta catalysts or with metallocene catalysts. “Linear” meansthat the polyethylene has few, if any, long chain branches, referred toas a g′_(vis) value of 0.97 or above, such as 0.98 or above.Polyethylenes having still greater density are the high densitypolyethylenes (“HDPEs”), e.g., polyethylenes having densities greaterthan 0.940 g/cm³, and are generally prepared with Ziegler-Nattacatalysts or chrome catalysts. Very low density polyethylenes (“VLDPEs”)can be produced by a number of different processes yieldingpolyethylenes having a density less than 0.916 g/cm³, such as 0.890g/cm³ to 0.915 g/cm³ or 0.900 g/cm³ to 0.915 g/cm³.

Polyolefins, such as polyethylene, which have high molecular weight,generally have desirable mechanical properties over their lowermolecular weight counterparts. However, high molecular weightpolyolefins can be difficult to process and can be costly to produce.Polyolefin compositions having a bimodal molecular weight distributionare desirable because they can combine the advantageous mechanicalproperties of a high molecular weight fraction of the composition withthe improved processing properties of a low molecular weight fraction ofthe composition.

Useful polyolefins, such as polyethylene, may have a comonomer, such ashexene, incorporated into the polyethylene backbone. These copolymersprovide varying physical properties compared to polyethylene alone andcan be produced in a low pressure reactor, utilizing, for example,solution, slurry, or gas phase polymerization processes. Polymerizationmay take place in the presence of catalyst systems such as thoseemploying a Ziegler-Natta catalyst, a chromium based catalyst, or ametallocene. The comonomer content of a polyolefin (e.g., wt % ofcomonomer incorporated into a polyolefin backbone) influences theproperties of the polyolefin (and composition of the copolymers) and isinfluenced by the polymerization catalyst.

A copolymer composition, such as a resin, has a compositiondistribution, which refers to the distribution of comonomer that formsshort chain branches along the copolymer backbone. When the amount ofshort chain branches varies among the copolymer molecules, thecomposition is said to have a “broad” composition distribution. When theamount of comonomer per 1,000 carbons is similar among the copolymermolecules of different chain lengths, the composition distribution issaid to be “narrow”.

Like comonomer content, the composition distribution influences theproperties of a copolymer composition, for example, stiffness,toughness, environmental stress crack resistance, and heat sealing,among other properties. The composition distribution of a polyolefincomposition may be readily measured by, for example, Temperature RisingElution Fractionation (TREF) or Crystallization Analysis Fractionation(CRYSTAF).

Polyolefin compositions may have broad composition distributions thatinclude a first polyolefin component having low molecular weight and lowcomonomer content while a second polyolefin component has a highmolecular weight and high comonomer content. Compositions having thisbroad orthogonal composition distribution in which the comonomer isincorporated predominantly in the high molecular weight chains canprovide improved physical properties, for example toughness propertiesand environmental stress crack resistance (ESCR).

Also, like comonomer content, a composition distribution of a copolymercomposition is influenced by the identity of the catalyst used to formthe polyolefins of the composition. Ziegler-Natta catalysts and chromiumbased catalysts generally produce compositions with broad compositiondistributions, whereas metallocene catalysts typically producecompositions with narrow composition distributions.

Nonetheless, polyolefin compositions formed by catalysts capable offorming high molecular weight polyolefins often also have broadmolecular weight distributions, as indicated by high polydispersityindices, and/or the polyolefins are of higher molecular weights (e.g.,Mw of 1,500,000) thus often have processing difficulties due tohardness. Furthermore, catalysts capable of forming high molecularweight polyolefins typically have low activity (e.g., amount ofdesirable polymer produced per a period of time).

There remains a need in the industry to improve the processability andthe stability of polymers and on developing new catalysts forpolymerization. Thus, there is a need for developing catalysts with arelatively high activity in order to form polyolefins, such aspolyethylene, with high molecular weight and narrow molecular weightdistribution, and high comonomer content.

References of interest include: Tshuva, E. Y. et al. (2000) J. Am. Chem.Soc. v. 122(43), pp. 10706-10707; WO 2002/036638A2; WO 2014/070502A1; WO2015/088819A1; WO 2018/022279A1; WO 2003/091262; U.S. Pat. No.8,071,701B2.

SUMMARY

The present disclosure provides ligand compounds and catalyst compoundsincluding a nonsymmetric bridged amine bis(phenolate) transition metalcomplex, production, and uses thereof. The bridged phenolate ligands arenonsymmetrical due in part to two linking diyl groups that are differentlengths.

This invention relates to ligands represented by Formula (I) and/ortransition metal complexes represented by Formula (II):

wherein:

M is a Group 4 transition metal;

Q¹ is a Group 15 atom;

Q² is a Group 15 atom or a Group 16 atom, wherein n is 0 if Q² is aGroup 16 atom or n is 1 if Q² is a Group 15 atom;

L¹ is

and is not part of an aromatic ring;

L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10;

each X¹ and X² is independently a substituted or unsubstituted linear,branched, cyclic, polycyclic, or aromatic hydrocarbyl; or X¹ and X² arejoined together to form a C₄-C₆₂ cyclic, polycyclic, heterocyclic, oraromatic group;

R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl;

each R² is independently a hydrogen, a substituted or unsubstitutedlinear, branched, cyclic, polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, ora heteroatom-containing group;

each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently a hydrogen, ahalogen, a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R³-R¹⁰ groups are joined together to forma C₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group;

each instance of R¹¹ is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and

each instance of R¹² is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.

In at least one embodiment, the present disclosure provides a catalystsystem that includes the catalyst, one or more activators, and anoptional catalyst support.

In at least one embodiment, the present disclosure provides apolymerization process that includes a) contacting one or more olefinmonomers with any of the catalyst systems discussed and describedherein.

In another embodiment, the present disclosure provides polymers havinghigh comonomer content, high molecular weight and narrow polydispersityindex, contributing to good processability for the polymer itself andfor the polymer used in a composition. Catalysts, catalyst systems, andprocesses of the present disclosure can provide catalyst activity valuesof 260 KgP/mmolCat·hr⁻¹ or greater and polyolefins, such as polyethylenecopolymers, having comonomer content of 12 wt % or greater, an Mn of150,000 g/mol or greater, an Mw of 250,000 g/mol or greater, and a Mw/Mnof 2.5 or less.

DETAILED DESCRIPTION

The present disclosure provides ligand compounds and catalyst compoundsincluding a nonsymmetric bridged amine bis(phenolate) transition metalcomplex, production, and uses thereof. In at least one embodiment, thepresent disclosure is directed to catalyst compounds, catalyst systems,and their use in polymerization processes to produce polyolefinpolymers, such as polyethylene polymers and polypropylene polymers. Inat least one embodiment, the present disclosure provides catalystcompounds including a nonsymmetric C₁,C₂-bridged ethylenediaminebis(phenolate), catalyst systems including such, and uses thereof.Catalyst compounds of the present disclosure can be zirconium orhafnium-containing compounds having one or more benzyl ligand(s)substituted and linked with a nonsymmetric C₁,C₂-bridged ethylenediaminebis(phenolate). In another class of embodiments, the present disclosureis directed to polymerization processes to produce polyolefin polymersfrom catalyst systems including one or more olefin polymerizationcatalysts, at least one activator, and an optional support.

For example, the present disclosure is directed to a polymerizationprocess to produce a polyethylene polymer, the process includingcontacting a catalyst system including one or more catalysts, at leastone activator, and at least one support, with ethylene and one or moreC₃-C₁₀ alpha-olefin comonomers under polymerization conditions.

Catalysts, catalyst systems, and processes of the present disclosure canprovide polyolefins at good activity values (e.g., 250 gP/mmolCat·h⁻¹ orgreater), high Mw (e.g., 650,000 g/mol or greater), Mn values of 450,000g/mol or greater, narrow PDI (e.g., about 2), and or Tm values of about85° C. or greater). Catalysts, catalyst systems, and processes of thepresent disclosure can provide polymers having a high comonomer content(e.g., 12 wt % or greater).

For the purposes of the present disclosure, the numbering scheme for thePeriodic Table Groups is used as described in Chemical and EngineeringNews, v. 63(5), pg. 27 (1985). Therefore, a “group 4 metal” is anelement from group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

The specification describes transition metal complexes. The term“complex” is used to describe molecules in which an ancillary ligand iscoordinated to a central transition metal atom. The ligand is bulky andstably bonded to the transition metal so as to maintain its influenceduring use of the catalyst, such as polymerization. The ligand may becoordinated to the transition metal by covalent bond and/or electrondonation coordination or intermediate bonds. The transition metalcomplexes are generally subjected to activation to perform theirpolymerization or oligomerization function using an activator which,without being bound by theory, is believed to create a cation as aresult of the removal of an anionic group, often referred to as aleaving group, from the transition metal.

A metallocene catalyst compound is a transition metal catalyst compoundhaving one, two or three, typically one or two, substituted orunsubstituted cyclopentadienyl ligands bound to the transition metal,typically a metallocene catalyst is an organometallic compoundcontaining at least one π-bound cyclopentadienyl moiety (or substitutedcyclopentadienyl moiety).

As used herein, “olefin polymerization catalyst(s)” refers to anycatalyst, such as an organometallic complex or compound that is capableof coordination polymerization addition where successive monomers areadded in a monomer chain at the organometallic active center.

The terms “substituent,” “radical,” “group,” and “moiety” may be usedinterchangeably.

As used herein, and unless otherwise specified, the term “Cn” meanshydrocarbon(s) having n carbon atom(s) per molecule, wherein n is apositive integer.

As used herein, and unless otherwise specified, the term “hydrocarbon”means a class of compounds containing hydrogen bound to carbon, andencompasses (i) saturated hydrocarbon compounds, (ii) unsaturatedhydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds(saturated and/or unsaturated), including mixtures of hydrocarboncompounds having different values of n.

“Catalyst productivity” is a measure of how many grams of polymer (P)are produced using a polymerization catalyst including W g of catalyst(cat), over a period of time of T hours; and may be expressed by thefollowing formula: P/(T×W) and expressed in units of gP/gcat/hr.Conversion is the amount of monomer that is converted to polymerproduct, and is reported as mol % and is calculated based on the polymeryield and the amount of monomer fed into the reactor. Catalyst activityis a measure of how active the catalyst is and is reported as the massof product polymer (P) produced per mole of catalyst (cat) used per hour(kgP/molcat/hr).

“BOCD” refers to a Broad Orthogonal Composition Distribution in whichthe comonomer of a copolymer is incorporated predominantly in the highmolecular weight chains or species of a polyolefin polymer orcomposition. The distribution of the short chain branches can bemeasured (as an indicator of comonomer content), for example, usingTemperature Rising Elution Fractionation (TREF) in connection with aLight Scattering (LS) detector to determine the weight average molecularweight of the molecules eluted from the TREF column at a giventemperature. The combination of TREF and LS (TREF-LS) yields informationabout the breadth of the composition distribution and whether thecomonomer content increases, decreases, or is uniform across the chainsof different molecular weights of polymer chains. BOCD has beendescribed, for example, in U.S. Pat. No. 8,378,043, Col. 3, line 34,bridging Col. 4, line 19, and U.S. Pat. No. 8,476,392, line 43, bridgingCol. 16, line 54.

An “olefin,” alternatively referred to as “alkene,” is a linear,branched, or cyclic compound of carbon and hydrogen having at least onedouble bond. For purposes of this specification and the claims appendedthereto, when a polymer or copolymer is referred to as including anolefin, the olefin present in such polymer or copolymer is thepolymerized form of the olefin. For example, when a copolymer is said tohave an “ethylene” content of 35 weight % (wt %) to 55 wt %, it isunderstood that the mer unit in the copolymer is derived from ethylenein the polymerization reaction and said derived units are present at 35wt % to 55 wt %, based upon the weight of the copolymer. A “polymer” hastwo or more of the same or different mer units. A “homopolymer” is apolymer having mer units that are the same. A “copolymer” is a polymerhaving two or more mer units that are different from each other. A“terpolymer” is a polymer having three mer units that are different fromeach other. Accordingly, the definition of copolymer, as used herein,includes terpolymers and the like. “Different” is used to refer to merunits indicates that the mer units differ from each other by at leastone atom or are different isomerically. An “ethylene polymer” or“ethylene copolymer” is a polymer or copolymer including at least 50 mol% ethylene derived units, a “propylene polymer” or “propylene copolymer”is a polymer or copolymer including at least 50 mol % propylene derivedunits, and so on.

Unless otherwise indicated, as used herein, “low comonomer content” isdefined as a polyolefin having less than 8 wt % of comonomer based uponthe total weight of the polyolefin. As used herein, “high comonomercontent” is defined as a polyolefin having greater than or equal to 8 wt% of comonomer based upon the total weight of the polyolefin.

For the purposes of the present disclosure, ethylene shall be consideredan α-olefin.

As used herein, Mn is number average molecular weight, Mw is weightaverage molecular weight, and Mz is z average molecular weight, wt % isweight percent, and mol % is mole percent. Molecular weight distribution(MWD), also referred to as polydispersity index (PDI), is defined to beMw divided by Mn. Unless otherwise noted, all molecular weight units(e.g., Mw, Mn, Mz) are g/mol.

Unless otherwise indicated, as used herein, “high molecular weight” isdefined as a number average molecular weight (Mn) value of 100,000 g/molor more. “Low molecular weight” is defined as an Mn value of less than100,000 g/mol.

Unless otherwise noted all melting points (Tm) are DSC second melt.

The following abbreviations may be used herein: dme is1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr ispropyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, cPR iscyclopropyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu ispara-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, DMAH-PFPB isN,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, TMS istrimethylsilyl, TIBAL is triisobutylaluminum, TNOAL istri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, Ph isphenyl, Bn is benzyl (i.e., CH₂Ph), Cbz is carbazole, THF (also referredto as thf) is tetrahydrofuran, RT is room temperature (and is 23° C.unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cyis cyclohexyl, Cp is cyclopentadienyl, Cp* is pentamethylcydopentadienyl, and Ind is indenyl.

A “catalyst system” includes at least one catalyst compound and at leastone activator. When “catalyst system” is used to describe such thecatalyst compound/activator combination before activation, it means theunactivated catalyst complex (precatalyst) together with an activatorand, optionally, a co-activator. When it is used to describe thecombination after activation, it means the activated complex and theactivator or other charge-balancing moiety. The transition metalcompound may be neutral as in a precatalyst, or a charged species with acounter ion as in an activated catalyst system. For the purposes of thepresent disclosure, when catalyst systems are described as includingneutral stable forms of the components, it is well understood by one ofordinary skill in the art, that the ionic form of the component is theform that reacts with the monomers to produce polymers. Furthermore,catalyst compounds represented by formulae herein embrace both neutraland ionic forms of the catalyst compounds.

In the description herein, the catalyst may be described as a catalystprecursor, a pre-catalyst compound, catalyst compound or a transitionmetal compound, and these terms are used interchangeably. Apolymerization catalyst system is a catalyst system that can polymerizemonomers to polymer. An “anionic ligand” is a negatively charged ligandwhich donates one or more pairs of electrons to a metal ion. A “neutraldonor ligand” is a neutrally charged ligand which donates one or morepairs of electrons to a metal ion. Activator and cocatalyst are alsoused interchangeably.

A scavenger is a compound that may be added to facilitate polymerizationby scavenging impurities. Some scavengers may also act as activators andmay be referred to as co-activators. A co-activator, that is not ascavenger, may also be used in conjunction with an activator in order toform an active catalyst. In at least one embodiment, a co-activator ispre-mixed with the transition metal compound to form an alkylatedtransition metal compound.

Non-coordinating anion (NCA) is an anion either that does not coordinateto the catalyst metal cation or that does coordinate to the metalcation, but only weakly. The term NCA is also defined to includemulticomponent NCA-containing activators, such as N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, that contain an acidic cationic groupand the non-coordinating anion. The term NCA is also defined to includeneutral Lewis acids, such as tris(pentafluorophenyl)boron, that canreact with a catalyst to form an activated species by abstraction of ananionic group. An NCA coordinates weakly enough that a neutral Lewisbase, such as an olefinically or acetylenically unsaturated monomer candisplace it from the catalyst center. Any metal or metalloid that canform a compatible, weakly coordinating complex may be used or containedin the non-coordinating anion. Suitable metals include, but are notlimited to, aluminum, gold, and platinum. Suitable metalloids include,but are not limited to, boron, aluminum, phosphorus, and silicon.

For purposes of the present disclosure, “alkoxides” include those wherethe alkyl group is a C₁ to C₁₀ hydrocarbyl. The alkyl group may bestraight chain, branched, or cyclic. The alkyl group may be saturated orunsaturated. In at least one embodiment, the alkyl group includes atleast one aromatic group.

The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,” areused interchangeably throughout this document. Likewise, the terms“group,” “radical,” and “substituent” are also used interchangeably inthis document. For purposes of this disclosure, “hydrocarbyl radical” isdefined to be C₁-C₁₀₀ radicals of carbon and hydrogen, that may belinear, branched, or cyclic, and when cyclic, aromatic or non-aromatic.Examples of such radicals can include methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl,hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, andcyclooctyl.

Unless indicated otherwise (e.g., the definition of “substitutedhydrocarbyl”), the term “substituted” means that at least one hydrogenatom has been replaced with at least one non-hydrogen group, such as ahydrocarbyl group, a heteroatom, or a heteroatom containing group, suchas halogen (such as Br, Cl, F or I) or a functional group such as —NR*₂,—OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃,—SnR*₃, —PbR*₃, and the like, where each R* is independently ahydrocarbyl or halocarbyl radical, and two or more R* may join togetherto form a substituted or unsubstituted completely saturated, partiallyunsaturated, or aromatic cyclic or polycyclic ring structure, or whereat least one heteroatom has been inserted within a hydrocarbyl ring. Asan example, ethyl alcohol is an ethyl group substituted with an —OHgroup.

The term “substituted hydrocarbyl” means a hydrocarbyl radical in whichat least one hydrogen atom of the hydrocarbyl radical has beensubstituted with at least one heteroatom (such as halogen, e.g., Br, Cl,F or I) or heteroatom-containing group (such as a functional group,e.g., —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂, —SbR*₂, —SR*, —BR*₂,—SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, and the like, where q is1 to 10 and each R* is independently a hydrocarbyl or halocarbylradical, and two or more R* may join together to form a substituted orunsubstituted completely saturated, partially unsaturated, or aromaticcyclic or polycyclic ring structure), or where at least one heteroatomhas been inserted within a hydrocarbyl ring.

For purposes of the present disclosure, in relation to catalystcompounds, the term “substituted” means that a hydrogen group has beenreplaced with a hydrocarbyl group, a heteroatom, or a heteroatomcontaining group, such as halogen (such as Br, Cl, F or I) or at leastone functional group such as —NR*₂, —OR*, —SeR*, —TeR*, —PR*₂, —AsR*₂,—SbR*₂, —SR*, —BR*₂, —SiR*₃, —GeR*₃, —SnR*₃, —PbR*₃, —(CH₂)q-SiR*₃, andthe like, where q is 1 to 10 and each R* is independently a hydrocarbylor halocarbyl radical, and two or more R* may join together to form asubstituted or unsubstituted completely saturated, partiallyunsaturated, or aromatic cyclic or polycyclic ring structure), or whereat least one heteroatom has been inserted within a hydrocarbyl ring.

The term “diyl,” “diyl group,” and “diyl radical” are usedinterchangeably throughout this disclosure. For purposes of thisdisclosure, “diyl” is defined to be C₁-C₄₀ divalent groups that may besubstituted or unsubstituted linear, branched, cyclic, polycyclic,heterocyclic, or aromatic. In examples throughout this disclosure, diylscan be or include, but are not limited to, C₁-C₄₀ diyls, C₁-C₂₅ diyls,C₁-C₁₈ diyls, C₁-C₁₂ diyls, C₁-C₁₀ diyls, and C₁-C₅ diyls. Examples of aC₁-C₅ diyl can be or include, but are not limited to, methanediyl(—CH₂—), ethanediyl (—CH₂CH₂—), propanediyl (—CH₂CH₂CH₂—), butanediyl(—CH₂(CH₂)₂CH₂—), and pentanediyl (—CH₂(CH₂)₃CH₂—), isomers thereof,halide substitutes thereof, or other substituted analogues thereof.

The term “substitutes thereof” means substituted analogues of thereferenced item(s), for example “C₁ to C₁₀ alkyls, and halidesubstitutes thereof,” means C₁ to C₁₀ alkyls and halide substitutedanalogs of the C₁ to C₁₀ alkyls.

The term “alkenyl” means a straight-chain, branched-chain, or cyclichydrocarbon radical having one or more double bonds. These alkenylradicals may be optionally substituted. Examples of suitable alkenylradicals can include ethenyl, propenyl, allyl, 1,4-butadienylcyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl,and the like, including their substituted analogues.

The term “arylalkenyl” means an aryl group where a hydrogen has beenreplaced with an alkenyl or substituted alkenyl group. For example,styryl indenyl is an indene substituted with an arylalkenyl group (astyrene group).

The terms “alkoxy” and “alkoxide” mean an alkyl or aryl group bound toan oxygen atom, such as an alkyl ether or aryl ether group/radicalconnected to an oxygen atom and can include those where the alkyl/arylgroup is a C₁ to C₁₀ hydrocarbyl. The alkyl group may be straight chain,branched, or cyclic. The alkyl group may be saturated or unsaturated.Examples of suitable alkoxy radicals can include methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,phenoxyl, and the like.

The term “aryl” or “aryl group” means a six carbon aromatic ring and thesubstituted variants thereof, such as phenyl, 2-methyl-phenyl, xylyl,4-bromo-xylyl. Likewise, heteroaryl means an aryl group where a ringcarbon atom (or two or three ring carbon atoms) has been replaced with aheteroatom, such as N, O, or S. As used herein, the term “aromatic” alsorefers to pseudoaromatic heterocycles which are heterocyclicsubstituents that have similar properties and structures (nearly planar)to aromatic heterocyclic ligands, but are not by definition aromatic;likewise the term aromatic also refers to substituted aromatics.

The term “arylalkyl” means an aryl group where a hydrogen has beenreplaced with an alkyl or substituted alkyl group. For example,3,5′-di-tert-butyl-phenyl indenyl is an indene substituted with anarylalkyl group.

The term “alkylaryl” means an alkyl group where a hydrogen has beenreplaced with an aryl or substituted aryl group. For example,ethylbenzyl indenyl is an indene substituted with an ethyl group boundto a benzyl group.

Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist(e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl) reference to onemember of the group (e.g., n-butyl) shall expressly disclose theremaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in thefamily. Likewise, reference to an alkyl, alkenyl, alkoxide, or arylgroup without specifying a particular isomer (e.g., butyl) expresslydiscloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, andtert-butyl).

The term “ring atom” means an atom that is part of a cyclic ringstructure. By this definition, a benzyl group has six ring atoms andtetrahydrofuran has 5 ring atoms.

A heterocyclic ring is a ring having a heteroatom in the ring structureas opposed to a heteroatom substituted ring where a hydrogen on a ringatom is replaced with a heteroatom. For example, tetrahydrofuran is aheterocyclic ring and 4-N,N-dimethylamino-phenyl is aheteroatom-substituted ring.

The term “continuous” means a system that operates without interruptionor cessation. For example, a continuous process to produce a polymerwould be one where the reactants are continually introduced into one ormore reactors and polymer product is continually withdrawn until thepolymerization is stopped, e.g. at 300 minutes.

A solution polymerization means a polymerization process in which thepolymer is dissolved in a liquid polymerization medium, such as an inertsolvent or monomer(s) or their blends. A solution polymerization ishomogeneous. A homogeneous polymerization is one where the polymerproduct is dissolved in the polymerization medium. Suitable systems maynot turbid as described in Oliveira, J. V. et al. (2000) Ind. Eng. Chem.Res., v. 39(12), pp. 4627-4633.

A bulk polymerization means a polymerization process in which themonomers and/or comonomers being polymerized are used as a solvent ordiluent using little or no inert solvent as a solvent or diluent. Asmall fraction of inert solvent might be used as a carrier for catalystand scavenger. A bulk polymerization system contains less than 25 wt %of inert solvent or diluent, such as less than 10 wt %, such as lessthan 1 wt %, such as 0 wt %.

U.S. Pat. No. 9,290,593 (593 patent) describes BOCD Index. The BOCDIndex may be described by the following equation:

BOCD Index=(Content of SCB at the high molecular weight side−Content ofSCB at the low molecular weight side)/(Content of SCB at the lowmolecular weight side),

where the “Content of SCB at the high molecular weight side” means thecontent of the SCB (the number of branches/1,000 carbon atoms) includedin a polymer chain having a molecular weight of Mw of the polyolefin ormore and 1.3×Mw or less, and the “Content of SCB at the low molecularweight side” means the content of the SCB (the number of branches/1,000carbon atoms) included in a polymer chain having a molecular weight of0.7×Mw of the polyolefin or more and less than Mw. The BOCD Indexdefined by the equation above may be in the range of 1 to 5, such as 2to 4, such as 2 to 3.5. See, also, FIG. 1 and FIG. 2 of the '593 patent(characterizing BOCD polymer structures using GPC-FTIR data).

The breadth of the composition distribution can be characterized by theT₇₅-T₂₅ value, where T₂₅ is the temperature at which 25% of the elutedpolymer is obtained and T₇₅ is the temperature at which 75% of theeluted polymer is obtained in a TREF experiment. The compositiondistribution is further characterized by the F₈₀ value, which is thefraction of polymer that elutes below 80° C. in a TREF-LS experiment. Ahigher F₈₀ value indicates a higher fraction of comonomer in the polymermolecule. An orthogonal composition distribution is defined by a M₆₀/M₉₀value that is greater than 1, where M₆₀ is the molecular weight of thepolymer fraction that elutes at 60° C. in a TREF-LS experiment and M₉₀is the molecular weight of the polymer fraction that elutes at 90° C. ina TREF-LS experiment.

In at least one embodiment, a polymer has a BOCD characterized in thatthe T₇₅-T₂₅ value is 1 or greater, 2 or greater, 2.5 or greater, 4 orgreater, 5 or greater, 7 or greater, 10 or greater, 11.5 or greater, 15or greater, 17.5 or greater, 20 or greater, 25 or greater, 30 orgreater, 35 or greater, 40 or greater, or 45 or greater, where T₂₅ isthe temperature at which 25% of the eluted polymer is obtained and T₇₅is the temperature at which 75% of the eluted polymer is obtained in aTREF experiment.

The polymers as described herein may further have a BOCD characterizedin that M₆₀/M₉₀ value is 1.5 or greater, 2 or greater, 2.25 or greater,2.5 or greater, 3 or greater, 3.5 or greater, 4 or greater, 4.5 orgreater, or 5 or greater, where M₆₀ is the molecular weight of thepolymer fraction that elutes at 60° C. in a TREF-LS experiment and M₉₀is the molecular weight of the polymer fraction that elutes at 90° C. ina TREF-LS experiment as described herein.

Additionally, the polymers as described herein may further have a BOCDcharacterized in that F₈₀ value is 1% or greater, 2% or greater, 3% orgreater, 4% or greater, 5% or greater, 6% or greater, 7% or greater, 10%or greater, 11% or greater, 12% or greater, or 15% or greater, where F₈₀is the fraction of polymer that elutes below 80° C.

Ligands

In at least one embodiment, the present disclosure provides one or moreligands that can be contained in a transition metal complex catalyst, asdiscussed and described herein. The ligand can be represented by Formula(I):

R¹ is a linker or bridge between the Q¹ and Q² groups. R¹ can be asubstituted or unsubstituted linear, branched, cyclic, polycyclic,heterocyclic, or aromatic diyl linking Q₁ and Q² groups. R¹ can be asubstituted or unsubstituted C₁-C₃₀ diyl, such as a substituted orunsubstituted C₁-C₁₈ diyl, a substituted or unsubstituted diyl, or asubstituted or unsubstituted C₁-C₅ diyl. In at least one embodiment, R¹is or includes an unsubstituted organic diyl group that can be orinclude methanediyl (—CH₂—), ethanediyl (—CH₂CH₂—), propanediyl(—CH₂CH₂CH₂—), butanediyl (—CH₂(CH₂)₂CH₂—), pentanediyl(—CH₂(CH₂)₃CH₂—), hexanediyl —CH₂(CH₂)₄CH₂—), heptanediyl(—CH₂(CH₂)₅CH₂—), octanediyl (—CH₂(CH₂)₆CH₂—), nonanediyl(—CH₂(CH₂)₇CH₂—), decanediyl (—CH₂(CH₂)₈CH₂—), undecanediyl(—CH₂(CH₂)₉CH₂—), dodecanediyl (—CH₂(CH₂)₁₀CH₂—), isomers thereof,halide substitutes thereof, or other substitutes thereof. In at leastone embodiment, R¹ is a substituted or unsubstituted linear or branchedC₁-C₅ diyl, such as an unsubstituted methanediyl, ethanediyl,propanediyl, a butanediyl, or a pentanediyl.

In at least one embodiment, R¹ is a substituted or unsubstituted cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ or C₁-C₁₀ diyl. R¹ can beor include a phenyl diyl, a benzyl diyl, a cyclohexyl diyl, a cyclooctyldiyl, or substitutes thereof. R¹ can be or include a substituted orunsubstituted heterocyclic diyl group that can be or include one or moreamines, ethers, thioethers, silyls, boryls, phosphines, or anycombination thereof.

In at least one embodiment, Q¹ is a Group 15 atom (e.g., N or P) and Q²is a Group 15 atom (e.g., N or P) or a Group 16 atom (e.g., 0, S, orSe), wherein n is 0 if Q² is a Group 16 atom or n is 1 if Q² is a Group15 atom. If Q² is a Group 16 atom, R³ is not present thereon. n can beeither 0 or 1, such as n is 0 if Q² is a Group 16 atom or n is 1 if Q²is a Group 15 atom. In at least one embodiment, Q¹ and Q² is N, or P,such as each of Q¹ and Q² is N.

The linker L¹ is a substituted or unsubstituted methanediyl group,

that is not part of an aromatic ring.

Each instance of R¹¹ is independently a hydrogen, a halogen (e.g., F,Br, Cl, or I), a substituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. In at least one embodiment,each R¹¹ is independently methyl, ethyl, ethenyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl,anthracenyl, carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl,imidazolyl, indenyl, indanyl, isomers thereof, halide substitutesthereof, or other substitutes thereof. The heteroatom-containing groupcan be or include amine, ether, thioether, silyl, boryl, phosphine, orany combination thereof. In at least one embodiment, two or moreadjacent R¹¹ groups are joined together to form a C₄-C₆₂ cyclic,polycyclic, or heterocyclic group that is not aromatic. In at least oneembodiment, two or more adjacent R¹¹ groups are joined together to forma C₆-C₆₂, C₁₀-050, or C₁₂-C₄₀ cyclic, polycyclic, or heterocyclic groupthat is not aromatic.

The linker L² is a substituted or unsubstituted organic diyl group,

that is not part of an aromatic ring. The substituted or unsubstitutedorganic diyl group can have two or more —C(R₁₂)₂— groups, such as y isan integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In at least oneembodiment, y is an integer in a range of 2 to 12, 2 to 10, 2 to 8, or 2to 5. In at least one embodiment, L² is methanediyl (—CH₂—), ethanediyl(—CH₂CH₂—), propanediyl (—CH₂CH₂CH₂—), butanediyl (—CH₂(CH₂)₂CH₂—),pentanediyl (—CH₂(CH₂)₃CH₂—), hexanediyl (—CH₂(CH₂)₄CH₂—), heptanediyl(—CH₂(CH₂)₅CH₂—), octanediyl (—CH₂(CH₂)₆CH₂—), nonanediyl(—CH₂(CH₂)₇CH₂—), decanediyl (—CH₂(CH₂)₈CH₂—), undecanediyl(—CH₂(CH₂)₉CH₂—), dodecanediyl (—CH₂(CH₂)₁₀CH₂—), isomers thereof, orhalide substitutes thereof. In at least one embodiment, L¹ is anunsubstituted methanediyl and L² can be a substituted or unsubstitutedethanediyl.

In at least one embodiment, for both L¹ and L², each instance of R¹¹ andR¹² is independently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl. In at least one embodiment, L² has y as an integer of 2, 3,4, or 5, and for both L¹ and L², each R¹¹ and R¹² is independently ahydrogen or a substituted or unsubstituted C₁-C₅ hydrocarbyl. In atleast one embodiment, y (of L²) is an integer of 2 or 3, each R¹¹ is ahydrogen, and each R¹² is independently a hydrogen or a substituted orunsubstituted C₁-C₃ hydrocarbyl.

The bridged bis(phenolate) ligand is nonsymmetrical due to the differentcarbon chain lengths of L¹ and L². L¹ is shorter than L² since L¹ is amethanediyl and L² is at least as long as an ethanediyl, or longer. Therelatively high catalytic activity of the catalyst (the transition metalcomplex) and/or the catalyst system is attributed, at least in part, tothe nonsymmetrical linkage or bridging caused by L¹ and L².

In at least one embodiment, each R² is independently a hydrogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. The substituted or unsubstituted C₁-C₄₀hydrocarbyl can be or include a substituted or unsubstituted linearC₁-C₄₀ hydrocarbyl, a substituted or unsubstituted branched C₃-C₄₀hydrocarbyl, or a substituted or unsubstituted cyclic, polycyclic, oraromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containing group can be orinclude amine, ether, thioether, silyl, boryl, phosphine, or anycombination thereof. In at least one embodiment, when Q² is N, each R²is independently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl.

In at least one embodiment, each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently a hydrogen, a halogen (e.g., F, Br, Cl, or I), asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, eachR³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ groups is or includes methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof. In at least one embodiment, two or more adjacent groups of R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ (R³-R¹⁰) are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group. In at leastone embodiment, two or more adjacent R³-R¹⁰ groups are joined togetherto form a C₆-C₆₂, C₁₀-C₅₀, or C₁₂-C₄₀ cyclic, polycyclic, heterocyclic,or aromatic group. In at least one embodiment, each of R⁴ and R⁸ is amethyl group.

In at least one embodiment, each of R⁶ and R¹⁰ is independently halogen,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof. R⁶ can be carbazolyl,fluorenyl, adamantyl, or a substitute thereof and R¹⁰ can be a halogen,such as Br. In at least one embodiment, each R⁵, R⁶, R⁷, R⁹, R¹⁰, andR¹¹ group is independently a hydrogen or a substituted or unsubstitutedlinear or branched C₁-C₁₀ hydrocarbyl. In at least one embodiment, eachR³, R⁵, R⁷, and R⁹ is a hydrogen and each R⁴ and R⁸ is a substituted orunsubstituted linear or branched C₁-C₄ hydrocarbyl.

In at least one embodiment, when the linker L¹ is an unsubstitutedmethanediyl group and the linker L² is an unsubstituted ethanediylgroup, then the ligand can be represented by the Formula (III):

In at least one embodiment, each R² is independently a hydrogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. The substituted or unsubstituted C₁-C₄₀hydrocarbyl can be or include a substituted or unsubstituted linearC₁-C₄₀ hydrocarbyl, a substituted or unsubstituted branched C₃-C₄₀hydrocarbyl, or a substituted or unsubstituted cyclic, polycyclic, oraromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containing group can be orinclude amine, ether, thioether, silyl, boryl, phosphine, or anycombination thereof. In at least one embodiment, each R² isindependently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl.

In at least one embodiment, each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently a hydrogen, a halogen (e.g., F, Br, Cl, or I), asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, eachR³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ groups is or includes methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof. In at least one embodiment, two or more adjacent groups of R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ (R³-R¹⁰) are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group. In at leastone embodiment, two or more adjacent R³-R¹⁰ groups are joined togetherto form a C₆-C₆₂, C₁₀-050, or C₁₂-C₄₀ cyclic, polycyclic, heterocyclic,or aromatic group. In at least one embodiment, each of R⁴ and R⁸ is amethyl group.

In at least one embodiment, each of R⁶ and R¹⁰ is independently halogen,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof. R⁶ can be carbazolyl,fluorenyl, adamantyl, or a substitute thereof and R¹⁰ can be a halogen,such as Br. In at least one embodiment, each R⁵, R⁶, R⁷, R⁹, and R¹⁰group is independently a hydrogen or a substituted or unsubstitutedlinear or branched C₁-C₁₀ hydrocarbyl. In at least one embodiment, eachR³, R⁵, R⁷, and R⁹ is a hydrogen and each R⁴ and R⁸ is a substituted orunsubstituted linear or branched C₁-C₄ hydrocarbyl.

The ligand represented by Formula (III) can be referred to as aC₁,C₂-bridged ligand.

In at least one embodiment, a ligand that is contained in a transitionmetal complex catalyst is represented by the Formula (IV):

In at least one embodiment, a ligand that is represented by Formula (I)is one or more of the following:

In at least one embodiment, a ligand that is represented by Formula (I)is:

Transition Metal Complexes

In at least one embodiment, the present disclosure relates to bridgedtransition metal complexes, where the complexes include at least one ofa C₄-C₆₂ cyclic or polycyclic ring structure with particularcombinations of substituents and bridged with, for example, anonsymmetric bridged ethylenediamine bis(phenolate). In at least oneembodiment, the bridge is characterized in that it has at least onefunctionality, either included in the bridge or bonded to it.

The invention relates to catalyst compounds, and catalyst systemsincluding such compounds, represented by formula (II):

The metal M can be any transition metal. In at least one embodiment, themetal M is a Group 4 transition metal, such as titanium, hafnium, orzirconium. In at least one embodiment, M is hafnium (Hf) or zirconium(Zr).

In at least one embodiment, each X¹ and X² is independently a hydrogen,a halogen (e.g., F, Br, Cl, or I), a substituted or unsubstituted C₁-C₄₀hydrocarbyl, or a heteroatom-containing group. A substituted orunsubstituted C₁-C₄₀ hydrocarbyl can be or include a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. A heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, X¹and X² are joined together to form a C₄-C₆₂ cyclic, polycyclic,heterocyclic, or aromatic group that is not aromatic. In at least oneembodiment, X¹ and X² are joined together to form a C₆-C₆₂, C₁₀-050, orC₁₂-C₄₀ cyclic, polycyclic, heterocyclic, or aromatic group.

In one or more examples, each X¹ and X² is independently a substitutedor unsubstituted C₁-C₂₀ hydrocarbyl. Each X¹ and X² can independently beor include a substituted or unsubstituted C₁-C₈ alkyl, a phenyl, abenzyl, a naphthyl, a cyclohexyl, or halide substitutes thereof. In atleast one embodiment, each X¹ and X² is benzyl.

R¹ is a linker or bridge between the Q¹ and Q² groups. R¹ can be asubstituted or unsubstituted linear, branched, cyclic, polycyclic,heterocyclic, or aromatic diyl linking Q¹ and Q² groups. R¹ can be asubstituted or unsubstituted C₁-C₃₀ diyl, such as a substituted orunsubstituted C₁-C₁₈ diyl, a substituted or unsubstituted C₁-C₁₀ diyl,or a substituted or unsubstituted C₁-C₅ diyl. In at least oneembodiment, R¹ is or includes an unsubstituted organic diyl group thatcan be or include methanediyl (—CH₂—), ethanediyl (—CH₂CH₂—),propanediyl (—CH₂CH₂CH₂—), butanediyl (—CH₂(CH₂)₂CH₂—), pentanediyl(—CH₂(CH₂)₃CH₂—), hexanediyl (—CH₂(CH₂)₄CH₂—), heptanediyl(—CH₂(CH₂)₅CH₂—), octanediyl (—CH₂(CH₂)₆CH₂—), nonanediyl(—CH₂(CH₂)₇CH₂—), decanediyl (—CH₂(CH₂)₈CH₂—), undecanediyl(—CH₂(CH₂)₉CH₂—), dodecanediyl (—CH₂(CH₂)₁₀CH₂—), isomers thereof,halide substitutes thereof, or other substitutes thereof. In at leastone embodiment, R¹ is a substituted or unsubstituted linear or branchedC₁-C₅ diyl, such as an unsubstituted methanediyl, ethanediyl,propanediyl, a butanediyl, or a pentanediyl.

In at least one embodiment, R¹ is a substituted or unsubstituted cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ or C₁-C₁₀ diyl. R¹ can beor include a phenyl diyl, a benzyl diyl, a cyclohexyl diyl, a cyclooctyldiyl, or substitutes thereof. R¹ can be or include a substituted orunsubstituted heterocyclic diyl group that can be or include one or moreamines, ethers, thioethers, silyls, boryls, phosphines, or anycombination thereof.

In at least one embodiment, Q¹ is a Group 15 atom (e.g., N or P) and Q²is a Group 15 atom (e.g., N or P) or a Group 16 atom (e.g., 0, S, orSe), wherein n is 0 if Q² is a Group 16 atom or n is 1 if Q² is a Group15 atom. If Q² is a Group 16 atom, R³ is not present thereon. n can beeither 0 or 1, such as n is 0 if Q² is a Group 16 atom or n is 1 if Q²is a Group 15 atom. In at least one embodiment, Q¹ and Q² is N, or P,such as each of Q¹ and Q² is N.

In at least one embodiment, the linker L¹ is a substituted orunsubstituted methanediyl group,

that is not part of an aromatic ring.

In at least one embodiment, each instance of R¹¹ is independently ahydrogen, a halogen (e.g., F, Br, Cl, or I), a substituted orunsubstituted C₁-C₄₀ hydrocarbyl, or a heteroatom-containing group. Inat least one embodiment, the substituted or unsubstituted C₁-C₄₀hydrocarbyl is or includes a substituted or unsubstituted linear C₁-C₄₀hydrocarbyl, a substituted or unsubstituted branched C₃-C₄₀ hydrocarbyl,or a substituted or unsubstituted cyclic, polycyclic, or aromatic C₄-C₄₀hydrocarbyl. In at least one embodiment, each R¹¹ is independentlymethyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl,cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl, anthracenyl,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, isomers thereof, halide substitutes thereof, or othersubstitutes thereof. The heteroatom-containing group can be or includeamine, ether, thioether, silyl, boryl, phosphine, or any combinationthereof. In at least one embodiment, two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic. In at least one embodiment, two or moreadjacent R¹¹ groups are joined together to form a C₆-C₆₂, C₁₀-C₅₀, orC₁₂-C₄₀ cyclic, polycyclic, or heterocyclic group that is not aromatic.

In at least one embodiment, the linker L² is a substituted orunsubstituted organic diyl group,

that is not part of an aromatic ring. The substituted or unsubstitutedorganic diyl group can have two or more —C(R₁₂)₂— groups, such as y isan integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. In at least oneembodiment, y is an integer in a range of 2 to 12, 2 to 10, 2 to 8, or 2to 5. In at least one embodiment, L² is methanediyl (—CH₂—), ethanediyl(—CH₂CH₂—), propanediyl (—CH₂CH₂CH₂—), butanediyl (—CH₂(CH₂)₂CH₂—),pentanediyl (—CH₂(CH₂)₃CH₂—), hexanediyl (—CH₂(CH₂)₄CH₂—), heptanediyl(—CH₂(CH₂)₅CH₂—), octanediyl (—CH₂(CH₂)₆CH₂—), nonanediyl(—CH₂(CH₂)₇CH₂—), decanediyl (—CH₂(CH₂)₈CH₂—), undecanediyl(—CH₂(CH₂)₉CH₂—), dodecanediyl (—CH₂(CH₂)₁₀CH₂—), isomers thereof, orhalide substitutes thereof. In at least one embodiment, L¹ is anunsubstituted methanediyl and L² can be a substituted or unsubstitutedethanediyl.

In at least one embodiment, for both L¹ and L², each instance of R¹¹ andR¹² is independently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl. In at least one embodiment, L² has y as an integer of 2, 3,4, or 5, and for both L¹ and L², each R¹¹ and R¹² is independently ahydrogen or a substituted or unsubstituted C₁-C₅ hydrocarbyl. In atleast one embodiment, y (of L²) is an integer of 2 or 3, each R¹¹ is ahydrogen, and each R¹² is independently a hydrogen or a substituted orunsubstituted C₁-C₃ hydrocarbyl.

The bridged bis(phenolate) ligand is nonsymmetrical due to the differentcarbon chain lengths of L¹ and L². L¹ is shorter than L² since L¹ is amethanediyl and L² is at least as long as an ethanediyl, or longer.Without wishing to be bound by theory, it is believed that therelatively high catalytic activity of the catalyst (the transition metalcomplex) and/or the catalyst system is attributed, at least in part, tothe nonsymmetrical linkage or bridging caused by L¹ and L².

In at least one embodiment, each R² is independently a hydrogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. The substituted or unsubstituted C₁-C₄₀hydrocarbyl can be or include a substituted or unsubstituted linearC₁-C₄₀ hydrocarbyl, a substituted or unsubstituted branched C₃-C₄₀hydrocarbyl, or a substituted or unsubstituted cyclic, polycyclic, oraromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containing group can be orinclude amine, ether, thioether, silyl, boryl, phosphine, or anycombination thereof. In at least one embodiment, when Q² is N, each R²is independently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl.

In at least one embodiment, each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently a hydrogen, a halogen (e.g., F, Br, Cl, or I), asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, eachR³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ groups is or includes methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof. In at least one embodiment, two or more adjacent groups of R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ (R³-R¹⁰) are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group. In at leastone embodiment, two or more adjacent R³-R¹⁰ groups are joined togetherto form a C₆-C₆₂, C₁₀-C₅₀, or C₁₂-C₄₀ cyclic, polycyclic, heterocyclic,or aromatic group. In at least one embodiment, each of R⁴ and R⁸ is amethyl group.

In at least one embodiment, each of R⁶ and R¹⁰ is independently halogen,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof. R⁶ can be carbazolyl,fluorenyl, adamantyl, or a substitute thereof and R¹⁰ can be a halogen,such as Br. In at least one embodiment, each R⁵, R⁶, R⁷, R⁹, R¹⁰, andR¹¹ group is independently a hydrogen or a substituted or unsubstitutedlinear or branched C₁-C₁₀ hydrocarbyl. In at least one embodiment, eachR³, R⁵, R⁷, and R⁹ is a hydrogen and each R⁴ and R⁸ is a substituted orunsubstituted linear or branched C₁-C₄ hydrocarbyl.

In at least one embodiment, when each Q¹ and Q² is a nitrogen, thelinker L¹ is an unsubstituted methanediyl group, and the linker L² is anunsubstituted ethanediyl group, then the transition metal complexcatalyst is represented by Formula (V):

The metal M can be any transition metal. In at least one embodiment, themetal M is a Group 4 transition metal, such as titanium, hafnium, orzirconium. In at least one embodiment, M is hafnium (Hf) or zirconium(Zr).

In at least one embodiment, each X¹ and X² is independently a hydrogen,a halogen (e.g., F, Br, Cl, or I), a substituted or unsubstituted C₁-C₄₀hydrocarbyl, or a heteroatom-containing group. A substituted orunsubstituted C₁-C₄₀ hydrocarbyl can be or include a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. A heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, X¹and X² are joined together to form a C₄-C₆₂ cyclic, polycyclic,heterocyclic, or aromatic group that is not aromatic. In at least oneembodiment, X¹ and X² are joined together to form a C₆-C₆₂, C₁₀-C₅₀, orC₁₂-C₄₀ cyclic, polycyclic, heterocyclic, or aromatic group.

In one or more examples, each X¹ and X² is independently a substitutedor unsubstituted C₁-C₄₀ hydrocarbyl. Each X¹ and X² can independently beor include a substituted or unsubstituted C₁-C₈ alkyl, a phenyl, abenzyl, a naphthyl, a cyclohexyl, or halide substitutes thereof. In atleast one embodiment, each X¹ and X² is benzyl.

In at least one embodiment, each R² is independently a hydrogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. The substituted or unsubstituted C₁-C₄₀hydrocarbyl can be or include a substituted or unsubstituted linearC₁-C₄₀ hydrocarbyl, a substituted or unsubstituted branched C₃-C₄₀hydrocarbyl, or a substituted or unsubstituted cyclic, polycyclic, oraromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containing group can be orinclude amine, ether, thioether, silyl, boryl, phosphine, or anycombination thereof. In at least one embodiment, each R² isindependently a hydrogen or a substituted or unsubstituted C₁-C₁₀hydrocarbyl.

In at least one embodiment, each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently a hydrogen, a halogen (e.g., F, Br, Cl, or I), asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, eachR³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ groups is or includes methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof. In at least one embodiment, two or more adjacent groups of R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ (R³-R¹⁰) are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group. In at leastone embodiment, two or more adjacent R³-R¹⁰ groups are joined togetherto form a C₆-C₆₂, C₁₀-C₅₀, or C₁₂-C₄₀ cyclic, polycyclic, heterocyclic,or aromatic group. In at least one embodiment, each of R⁴ and R⁸ is amethyl group.

In at least one embodiment, each of R⁶ and R¹⁰ is independently halogen,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof. R⁶ can be carbazolyl,fluorenyl, adamantyl, or a substitute thereof and R¹⁰ can be a halogen,such as Br. In at least one embodiment, each R⁵, R⁶, R⁷, R⁹, and R¹⁰group is independently a hydrogen or a substituted or unsubstitutedlinear or branched C₁-C₁₀ hydrocarbyl. In at least one embodiment, eachR³, R⁵, R⁷, and R⁹ is a hydrogen and each R⁴ and R⁸ is a substituted orunsubstituted linear or branched C₁-C₄ hydrocarbyl.

The ligand represented by Formula (V) can be referred to as aC₁,C₂-bridged catalyst compound.

In at least one embodiment, when each Q¹ and Q² is a nitrogen, thelinker L¹ is an unsubstituted methanediyl group, the linker L² is anunsubstituted ethanediyl group, and R¹ is an unsubstituted ethanediylgroup, then the transition metal complex catalyst is represented by(VI):

The metal M can be any transition metal. In at least one embodiment, themetal M is a Group 4 transition metal, such as titanium, hafnium, orzirconium. In at least one embodiment, M is hafnium (Hf) or zirconium(Zr).

In at least one embodiment, each X¹ and X² is independently a hydrogen,a halogen (e.g., F, Br, Cl, or I), a substituted or unsubstituted C₁-C₄₀hydrocarbyl, or a heteroatom-containing group. A substituted orunsubstituted C₁-C₄₀ hydrocarbyl can be or include a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. A heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, X¹and X² are joined together to form a C₄-C₆₂ cyclic, polycyclic,heterocyclic, or aromatic group that is not aromatic. In at least oneembodiment, X¹ and X² are joined together to form a C₆-C₆₂, C₁₀-050, orC₁₂-C₄₀ cyclic, polycyclic, heterocyclic, or aromatic group.

In one or more examples, each X¹ and X² is independently a substitutedor unsubstituted C₁-C₂₀ hydrocarbyl. Each X¹ and X² can independently beor include a substituted or unsubstituted C₁-C₈ alkyl, a phenyl, abenzyl, a naphthyl, a cyclohexyl, or halide substitutes thereof. In atleast one embodiment, each X¹ and X² is benzyl.

In at least one embodiment, each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently a hydrogen, a halogen (e.g., F, Br, Cl, or I), asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group. In at least one embodiment, the substitutedor unsubstituted C₁-C₄₀ hydrocarbyl is or includes a substituted orunsubstituted linear C₁-C₄₀ hydrocarbyl, a substituted or unsubstitutedbranched C₃-C₄₀ hydrocarbyl, or a substituted or unsubstituted cyclic,polycyclic, or aromatic C₄-C₄₀ hydrocarbyl. The heteroatom-containinggroup can be or include amine, ether, thioether, silyl, boryl,phosphine, or any combination thereof. In at least one embodiment, eachR³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ groups is or includes methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof. In at least one embodiment, two or more adjacent groups of R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ (R³-R¹⁰) are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group. In at leastone embodiment, two or more adjacent R³-R¹⁰ groups are joined togetherto form a C₆-C₆₂, C₁₀-050, or C₁₂-C₄₀ cyclic, polycyclic, heterocyclic,or aromatic group. In at least one embodiment, each of R⁴ and R⁸ is amethyl group.

In at least one embodiment, each of R⁶ and R¹⁰ is independently halogen,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof. R⁶ can be carbazolyl,fluorenyl, adamantyl, or a substitute thereof and R¹⁰ can be a halogen,such as Br. In at least one embodiment, each R⁵, R⁶, R⁷, R⁹, and R¹⁰group is independently a hydrogen or a substituted or unsubstitutedlinear or branched C₁-C₁₀ hydrocarbyl. In at least one embodiment, eachR³, R⁵, R⁷, and R⁹ is a hydrogen and each R⁴ and R⁸ is a substituted orunsubstituted linear or branched C₁-C₄ hydrocarbyl.

In at least one embodiment, the transition metal complex catalyst isrepresented by Formula (VII):

wherein M is Zr or Hf. When M is Zr, the compound of Formula (VII) isreferred to as Zr-VII. When M is Hf, the compound of Formula (VII) isreferred to as Hf-VII.

In at least one embodiment, a transition metal complex catalyst isrepresented by Formula (II) is one or more of the following:

In preferred embodiments of the invention, the transition metal complexcatalyst is represented by Formula (II) is one or more of the following:

Methods to Prepare the Catalyst Compounds

Ligands of Formulas (I), (III) and (IV) may be synthesized according tothe schematic reaction procedure described in Schemes 1-3. Transitionmetal complex catalysts of Formulas (II), (VI) and (VII) can besynthesized according to the schematic reaction procedure described inScheme 4.

As shown in Scheme 1: (i) 2-carbazolyl-4-methylphenol is treated withparaformaldehyde to produce 2-carbazolyl-4-methyl-5-methenyl-oxo-phenol;(ii) 2-carbazolyl-4-methyl-6-methenyl-oxo-phenol is treated withN,N-dimethylethylenediamine to produce Compound A2-carbazolyl-4-methyl-6-methene-(N,N-dimethyl-ethylenediamine)-phenol.

As shown in Scheme 2: (i) 2-bromo-4-methylphenol is treated with allylbromide to produce 1-(allyloxy)-2-bromo-4-methylbenzene; (ii)1-(allyloxy)-2-bromo-4-methylbenzene is heated to produce2-bromo-4-methyl-6-allylphenol; (iii) 2-bromo-4-methyl-6-allylphenol istreated with methoxymethyl chloride to produce1-(MOM-oxy)-2-bromo-4-methyl-5-allylbenzene; and (iv)1-(MOM-oxy)-2-bromo-4-methyl-6-allylbenzene is treated with ozone toproduce Compound B 1-(MOM-oxy)-2-bromo-4-methyl-6-propenyl-oxo-benzene.

As shown in Scheme 3: Compound A2-carbazolyl-4-methyl-6-methene-(N,N-dimethyl-ethylenediamine)-phenoland Compound B 1-(MOM-oxy)-2-bromo-4-methyl-6-propenyl-oxo-benzene arecombined and reacted to produce the ligand of Formula (IV).

As shown in Scheme 4: The ligand of Formula (IV) and a tetrabenzyl metal(Zr or Hf) are combined and reacted to produce the transition metalcomplex catalysts of Formula (VII), where M is zirconium or hafnium.

Activators

The terms “cocatalyst” and “activator” are used herein interchangeablyand are defined to be any compound which can activate any one of thecatalyst compounds described above by converting the neutral catalystcompound to a catalytically active catalyst compound cation.

After the catalysts have been synthesized, catalyst systems may beformed by combining the catalysts with activators in any suitablemanner, including by supporting them for use in slurry or gas phasepolymerization. The catalyst systems may also be added to or generatedin solution polymerization or bulk polymerization (in the monomer, suchas, without solvent). Suitable catalyst system may contain a transitionmetal complex as described above and an activator such as alumoxane or anon-coordinating anion activator. Activation may be performed usingalumoxane solution including an alkyl alumoxane such as methylalumoxane, referred to as MAO, as well as modified MAO, referred toherein as MMAO, which contains some higher alkyl groups to improve thesolubility. MAO can be purchased from Albemarle Corporation, BatonRouge, La., such as in a 10 wt % solution in toluene. In at least oneembodiment, activators that is used in the catalyst system is orincludes one or more alumoxanes, one or more aluminum alkyls, and otheraluminum compounds. Suitable activators that can be used in the catalystsystem can be or include, but are not limited to, methyl alumoxane,ethyl alumoxane, isobutyl alumoxane, isobutyl alumoxane, trimethylaluminum, triethyl aluminum, tripropyl aluminum, tributyl aluminum,N,N-dimethylanilinium tetra(perfluorophenyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)b orate, triphenylcarbeniumtetra(perfluorophenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate,1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium,tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine, isomersthereof, substitutes thereof, or any combination thereof.

When an alumoxane or modified alumoxane is used, thecatalyst-to-activator molar ratio is from about 1:3,000 to about 10:1;such as about 1:2,000 to about 10:1; such as about 1:1,000 to about10:1; such as about 1:500 to about 1:1; such as about 1:300 to about1:1; such as about 1:200 to about 1:1; such as about 1:100 to about 1:1;such as about 1:50 to about 1:1; such as about 1:10 to about 1:1. Whenthe activator is an alumoxane (modified or unmodified), some embodimentsselect the maximum amount of activator at a 5,000-fold molar excess overthe catalyst (per metal catalytic site). The minimumactivator-to-catalyst ratio can be 1:1 molar ratio.

Activation may also be performed using non-coordinating anions, referredto as NCA's, of the type, such as described in EP0277003A1 andEP0277004A1. NCA may be added in the form of an ion pair using, such as[DMAH]+[NCA]− in which the N,N-dimethylanilinium (DMAH) cation reactswith a basic leaving group on the transition metal complex to form atransition metal complex cation and [NCA]−. The cation in the precursormay, alternatively, be trityl. Alternatively, the transition metalcomplex may be reacted with a neutral NCA precursor, such as B(C₆F₅)₃,which abstracts an anionic group from the complex to form an activatedspecies. Suitable activators include N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate ([PhNMe₂H]B(C₆F₅)₄) and N,N-dimethylaniliniumtetrakis (heptafluoronaphthyl)borate, where Ph is phenyl, and Me ismethyl.

Additionally, activators useful herein include those described in U.S.Pat. No. 7,247,687 at column 169, line 50 to column 174, line 43,particularly column 172, line 24 to column 173, line 53.

In at least one embodiment of the present disclosure described herein,the non-coordinating anion activator is represented by the followingformula (1):

(Z)^(d+)(A^(d−))  (1)

where Z is (L-H) or a reducible Lewis acid, L is a neutral Lewis base, His hydrogen and (L-H)⁺ is a Brønsted acid; A^(d−) is a non-coordinatinganion having the charge d−; and d is an integer from 1 to 3.

When Z is (L-H) such that the cation component is (L-H)^(d+), the cationcomponent may include Brønsted acids such as protonated Lewis basescapable of protonating a moiety, such as an alkyl or aryl, from thecatalyst precursor, resulting in a cationic transition metal species, orthe activating cation (L-H)^(d+) is a Brønsted acid, capable of donatinga proton to the catalyst precursor resulting in a transition metalcation, including ammoniums, oxoniums, phosphoniums, silyliums, andmixtures thereof, or ammoniums of methylamine, aniline, dimethylamine,diethylamine, N-methylaniline, diphenylamine, trimethylamine,triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniumsfrom triethylphosphine, triphenylphosphine, and diphenylphosphine,oxoniums from ethers, such as dimethyl ether diethyl ether,tetrahydrofuran, and dioxane, sulfoniums from thioethers, such asdiethyl thioethers and tetrahydrothiophene, and mixtures thereof.

When Z is a reducible Lewis acid, it may be represented by the formula:(Ar₃C⁺), where Ar is aryl or aryl substituted with a heteroatom, or a C₁to C₄₀ hydrocarbyl, the reducible Lewis acid may be represented by theformula: (Ph₃C⁺), where Ph is phenyl or phenyl substituted with aheteroatom, and/or a C₁ to C₄₀ hydrocarbyl. In at least one embodiment,the reducible Lewis acid is triphenyl carbenium.

In at least one embodiment, the anion component A^(d−) includes thosehaving the formula [M^(k)+Q^(n)]^(d−) where k is 1, 2, or 3; n is 1, 2,3, 4, 5 or 6, or 3, 4, 5 or 6; n−k=d; M is an element selected fromGroup 13 of the Periodic Table of the Elements, or boron or aluminum,and Q is independently a hydride, bridged or unbridged dialkylamido,halide, alkoxide, aryloxide, hydrocarbyl radicals, the Q having up to 20carbon atoms with the proviso that in not more than one occurrence is Qa halide, and two Q groups may form a ring structure. Each Q may be afluorinated hydrocarbyl radical having 1 to 20 carbon atoms, or each Qis a fluorinated aryl radical, or each Q is a pentafluoryl aryl radical.Examples of suitable Ad-components also include diboron compounds asdisclosed in U.S. Pat. No. 5,447,895, which is fully incorporated hereinby reference.

In at least one embodiment, in any of the NCA's represented by Formula(1) described above, the anion component Ad− is represented by theformula [M*k*+Q*n*]d*− where k* is 1, 2, or 3; n* is 1, 2, 3, 4, 5, or 6(or 1, 2, 3, or 4); n*−k*=d*; M* is boron; and Q* is independentlyselected from hydride, bridged or unbridged dialkylamido, halogen,alkoxide, aryloxide, hydrocarbyl radicals, the Q* having up to 20 carbonatoms with the proviso that in not more than 1 occurrence is Q* ahalogen.

The present disclosure also provides a method to polymerize olefinsincluding contacting olefins (such as propylene) with a catalyst complexas described above and an NCA activator represented by the Formula (2):

R_(n)M**(ArNHal)^(4-n)  (2)

where R is a monoanionic ligand; M** is a Group 13 metal or metalloid;ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclicaromatic ring, or aromatic ring assembly in which two or more rings (orfused ring systems) are joined directly to one another or together; andn is 0, 1, 2, or 3. For example, the NCA containing an anion of Formula(2) also contains a suitable cation that is essentially non-interferingwith the ionic catalyst complexes formed with the transition metalcompounds, or the cation is Zd+ as described above.

In at least one embodiment, in any of the NCA's containing an anionrepresented by Formula (2) described above, R is selected from the groupconsisting of C₁ to C₃₀ hydrocarbyl radicals. In at least oneembodiment, C₁ to C₃₀ hydrocarbyl radicals is substituted with one ormore C₁ to C₂₀ hydrocarbyl radicals, halide, hydrocarbyl substitutedorganometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido,arylsulfido, alkylphosphido, arylphosphide, or other anionicsubstituent; fluoride; bulky alkoxides, where bulky means C₄ to C₂₀hydrocarbyl radicals; —SRa, —NRa₂, and —PRa₂, where each Ra isindependently a monovalent C₄ to C₂₀ hydrocarbyl radical having amolecular volume greater than or equal to the molecular volume of anisopropyl substitution or a C₄ to C₂₀ hydrocarbyl substitutedorganometalloid having a molecular volume greater than or equal to themolecular volume of an isopropyl substitution.

In at least one embodiment, in any of the NCA's containing an anionrepresented by Formula (2) described above, the NCA also includes cationcontaining a reducible Lewis acid represented by the formula: (Ar₃C⁺),where Ar is aryl or aryl substituted with a heteroatom, and/or a C₁ toC₄₀ hydrocarbyl, or the reducible Lewis acid represented by the formula:(Ph₃C⁺), where Ph is phenyl or phenyl substituted with one or moreheteroatoms, and/or C₁ to C₄₀ hydrocarbyls.

In at least one embodiment, in any of the NCA's containing an anionrepresented by Formula (2) described above, the NCA also contains acation represented by the formula, (L-H)^(d+), wherein L is an neutralLewis base; H is hydrogen; (L-H) is a Brønsted acid; and d is 1, 2, or3, or (L-H)^(d+) is a Brønsted acid selected from ammoniums, oxoniums,phosphoniums, silyliums, and mixtures thereof.

In at least one embodiment, suitable activators include those disclosedin U.S. Pat. Nos. 7,297,653 and 7,799,879, which are fully incorporatedby reference herein.

In at least one embodiment, an activator is or includes a salt of acationic oxidizing agent and a noncoordinating, compatible anionrepresented by the Formula (3):

(OX^(e+))_(d)(A^(d−))_(e)  (3)

where OX^(e+) is a cationic oxidizing agent having a charge of e+; e is1, 2 or 3; d is 1, 2 or 3; and A^(d−) is a non-coordinating anion havingthe charge of d− (as further described above). Examples of cationicoxidizing agents include: ferrocenium, hydrocarbyl-substitutedferrocenium, Ag⁺, or Pb²⁺. Suitable embodiments of A^(d−) includetetrakis(pentafluorophenyl)borate.

Suitable activators useful in catalyst systems can be or include one ormore of: trimethylammonium tetrakis(perfluoronaphthyl)borate,N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,triphenylcarbenium tetrakis(perfluoronaphthyl)borate, trimethylammoniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, and the types disclosed in U.S. Pat.No. 7,297,653, which is fully incorporated by reference herein.

Suitable activators may also include: N,N-dimethylaniliniumtetrakis(perfluoronaphthyl)borate, N,N-dimethylaniliniumtetrakis(perfluorobiphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbeniumtetrakis(perfluorophenyl)borate, [Ph₃C⁺][B(C₆F₅)₄ ⁻], [Me₃NH⁺][B(C₆F₅)₄⁻];1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidinium;and tetrakis(pentafluorophenyl)borate,4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridine.

In at least one embodiment, the activator is or includes one or more ofa triaryl carbonium (such as triphenylcarbenium tetraphenylborate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbeniumtetrakis(perfluoronaphthyl)borate, triphenylcarbeniumtetrakis(perfluorobiphenyl)borate, triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate).

In at least one embodiment, an activator is or includes one or more ofN,N-dimethylanilinium tetra(perfluorophenyl)borate;N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate;N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate;N,N-dimethylaniliniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate;triphenylcarbenium tetrakis(perfluoronaphthyl)borate; triphenylcarbeniumtetrakis(perfluorobiphenyl)borate; triphenylcarbeniumtetrakis(3,5-bis(trifluoromethyl)phenyl)borate; triphenylcarbeniumtetra(perfluorophenyl)borate; trimethylammoniumtetrakis(perfluoronaphthyl)borate; triethylammoniumtetrakis(perfluoronaphthyl)borate; tripropylammoniumtetrakis(perfluoronaphthyl)borate; tri(n-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; tri(t-butyl)ammoniumtetrakis(perfluoronaphthyl)borate; N,N-diethylaniliniumtetrakis(perfluoronaphthyl)borate;N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis(perfluoronaphthyl)borate; and tropilliumtetrakis(perfluoronaphthyl)borate.

In at least one embodiment, two NCA activators is used in thepolymerization and the molar ratio of the first NCA activator to thesecond NCA activator is any ratio. In at least one embodiment, the molarratio of the first NCA activator to the second NCA activator is 0.01:1to 10,000:1, or 0.1:1 to 1,000:1, or 1:1 to 100:1.

In at least one embodiment, the NCA activator-to-catalyst ratio is a 1:1molar ratio, or 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1 or1:1 to 1,000:1. In at least one embodiment, the NCAactivator-to-catalyst ratio is 0.5:1 to 10:1, or 1:1 to 5:1.

In at least one embodiment, the transition metal complex catalysts iscombined with combinations of alumoxanes and NCA's (see for example,U.S. Pat. Nos. 5,153,157, 5,453,410, EP 0573120B1, WO 1994/007928, andWO 1995/014044 which discuss the use of an alumoxane in combination withan ionizing activator, all of which are incorporated by referenceherein).

In at least one embodiment, when an NCA (such as an ionic or neutralactivator) is used, suitable catalyst-to-activator molar ratio can befrom 1:10 to 1:1; 1:10 to 10:1; 1:10 to 2:1; 1:10 to 3:1; 1:10 to 5:1;1:2 to 1.2:1; 1:2 to 10:1; 1:2 to 2:1; 1:2 to 3:1; 1:2 to 5:1; 1:3 to1.2:1; 1:3 to 10:1; 1:3 to 2:1; 1:3 to 3:1; 1:3 to 5:1; 1:5 to 1:1; 1:5to 10:1; 1:5 to 2:1; 1:5 to 3:1; 1:5 to 5:1; 1:1 to 1:1.2.

Likewise, a co-activator, such as a group 1, 2, or 13 organometallicspecies (e.g., an alkyl aluminum compound such as tri-n-octyl aluminum),may be used in the catalyst system herein. The catalyst-to-co-activatormolar ratio is from 1:100 to 100:1; 1:75 to 75:1; 1:50 to 50:1; 1:25 to25:1; 1:15 to 15:1; 1:10 to 10:1; 1:5 to 5:1; 1:2 to 2:1; 1:100 to 1:1;1:75 to 1:1; 1:50 to 1:1; 1:25 to 1:1; 1:15 to 1:1; 1:10 to 1:1; 1:5 to1:1; 1:2 to 1:1; 1:10 to 2:1.

Support Materials

In at least one embodiment, the catalyst system includes an inertsupport material. In at least one embodiment, the supported material isa porous support material, for example, talc, or inorganic oxides. Othersupport materials include zeolites, clays, organoclays, or any othersuitable organic or inorganic support material and the like, or mixturesthereof.

In at least one embodiment, the support material is an inorganic oxide.Suitable inorganic oxide materials for use in transition metal complexcatalyst systems herein include Groups 2, 4, 13, and 14 metal oxides,such as silica, alumina, and mixtures thereof. Other inorganic oxidesthat may be employed either alone or in combination with the silica, oralumina are magnesia, titania, zirconia, and the like. Other suitablesupport materials, however, can be employed, such as functionalizedpolyolefins, such as polyethylene. Supports include magnesia, titania,zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, andthe like. Also, combinations of these support materials may be used,such as silica-chromium, silica-alumina, silica-titania, and the like.Support materials can be or include, but are not limited to Al₂O₃, ZrO₂,SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay, silicon oxide/clay, or anymixture thereof.

The support material, such as an inorganic oxide, can have a surfacearea in the range of from about 10 m²/g to about 700 m²/g, pore volumein the range of from about 0.1 cm³/g to about 4 cm³/g and averageparticle size in the range of from about 5 μm to about 500 μm. In atleast one embodiment, the surface area of the support material is in therange of from about 50 m²/g to about 500 m²/g, pore volume of from about0.5 cm³/g to about 3.5 cm³/g and average particle size of from about 10μm to about 200 μm. In at least one embodiment, the surface area of thesupport material is in the range of from about 100 m²/g to about 400m²/g, pore volume from about 0.8 cm³/g to about 3 cm³/g and averageparticle size is from about 5 μm to about 100 μm. The average pore sizeof the support material useful in the present disclosure is in the rangeof from 10 Å to 1,000 Å, such as 50 Å to about 500 Å, such as 75 Å toabout 350 Å. In at least one embodiment, the support material is a highsurface area, amorphous silica (surface area=300 m²/gm; pore volume of1.65 cm³/gm). Silicas are marketed under the tradenames of DAVISON 952or DAVISON 955 by the Davison Chemical Division of W.R. Grace andCompany. In other embodiments DAVISON 948 is used. Alternatively, asilica can be ES-70™ silica (PQ Corporation, Malvern, Pa.) that haspreferably been calcined (such as at 875° C.).

The support material should be dry, that is, substantially free ofabsorbed water. Drying of the support material can be effected byheating or calcining at about 100° C. to about 1,000° C., such as atleast about 600° C. When the support material is silica, it is heated toat least 200° C., such as about 200° C. to about 850° C., such as atabout 600° C.; and for a time of about 1 minute to about 100 hours, fromabout 12 hours to about 72 hours, or from about 24 hours to about 60hours. The calcined support material should have at least some reactivehydroxyl (OH) groups to produce supported catalyst systems of thepresent disclosure. The calcined support material is then contacted withat least one polymerization catalyst containing one or more transitionmetal complex catalyst and an activator.

The support material, having reactive surface groups, such as hydroxylgroups, is slurried in a non-polar solvent and the resulting slurry iscontacted with a solution of a transition metal complex catalyst and anactivator. In at least one embodiment, the slurry of the supportmaterial is first contacted with the activator for a period of time inthe range of from about 0.5 hours to about 24 hours, from about 2 hoursto about 16 hours, or from about 4 hours to about 8 hours. The solutionof the transition metal complex catalyst is then contacted with theisolated support/activator. In at least one embodiment, the supportedcatalyst system is generated in situ. The slurry of the support materialcan be first contacted with the catalyst compound for a period of timein the range of from about 0.5 hours to about 24 hours, from about 2hours to about 16 hours, or from about 4 hours to about 8 hours. Theslurry of the supported transition metal complex catalyst is thencontacted with the activator solution.

The mixture of the catalyst, activator and support is heated to about 0°C. to about 70° C., such as to about 23° C. to about 60° C., such as atroom temperature. Suitable contact times can range from about 0.5 hoursto about 24 hours, from about 2 hours to about 16 hours, or from about 4hours to about 8 hours.

Suitable non-polar solvents are materials in which all of the reactantsused herein, e.g., the activator, and the catalyst compound, are atleast partially soluble and which are liquid at room temperature.Non-limiting example non-polar solvents are alkanes, such as isopentane,hexane, n-heptane, octane, nonane, and decane, cycloalkanes, such ascyclohexane, aromatics, such as benzene, toluene, and ethylbenzene.

In at least one embodiment, the support material contains a supportmaterial treated with an electron-withdrawing anion. The supportmaterial can be silica, alumina, silica-alumina, silica-zirconia,alumina-zirconia, aluminum phosphate, heteropolytungstates, titania,magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereofand the electron-withdrawing anion is selected from fluoride, chloride,bromide, phosphate, triflate, bisulfate, sulfate, or any combinationthereof.

The electron-withdrawing component used to treat the support materialcan be any component that increases the Lewis or Brønsted acidity of thesupport material upon treatment (as compared to the support materialthat is not treated with at least one electron-withdrawing anion). In atleast one embodiment, the electron-withdrawing component is anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Electron-withdrawing anions can be sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, phospho-tungstate, or mixtures thereof,or combinations thereof. An electron-withdrawing anion can be fluoride,chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or anycombination thereof, at least one embodiment of this disclosure. In atleast one embodiment, the electron-withdrawing anion is sulfate,bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate,fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate,fluorozirconate, fluorotitanate, or combinations thereof.

Thus, for example, the support material suitable for use in the catalystsystems of the present disclosure can be one or more of fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or combinations thereof. In one or more embodiments, theactivator-support can be or include fluorided alumina, sulfated alumina,fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or combinations thereof. In another embodiment,the support material includes alumina treated with hexafluorotitanicacid, silica-coated alumina treated with hexafluorotitanic acid,silica-alumina treated with hexafluorozirconic acid, silica-aluminatreated with trifluoroacetic acid, fluorided boria-alumina, silicatreated with tetrafluoroboric acid, alumina treated withtetrafluoroboric acid, alumina treated with hexafluorophosphoric acid,or combinations thereof. Further, any of these activator-supportsoptionally can be treated with a metal ion.

Nonlimiting examples of cations suitable for use in the presentdisclosure in the salt of the electron-withdrawing anion includeammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkylphosphonium, H+, [H(OEt₂)₂]+, or combinations thereof.

Further, combinations of one or more different electron-withdrawinganions, in varying proportions, can be used to tailor the specificacidity of the support material to a desired level. Combinations ofelectron-withdrawing components can be contacted with the supportmaterial simultaneously or individually, and in any order that providesa desired chemically-treated support material acidity. For example, inone or more embodiments, two or more electron-withdrawing anion sourcecompounds in two or more separate contacting steps.

In at least one embodiment, a process by which a chemically-treatedsupport material is prepared can include contacting a selected supportmaterial, or combination of support materials, with a firstelectron-withdrawing anion source compound to form a first mixture; suchfirst mixture can be calcined and then contacted with a secondelectron-withdrawing anion source compound to form a second mixture; thesecond mixture can then be calcined to form a treated support material.In such a process, the first and second electron-withdrawing anionsource compounds can be either the same or different compounds.

The method by which the oxide is contacted with the electron-withdrawingcomponent, such as a salt or an acid of an electron-withdrawing anion,can include gelling, co-gelling, impregnation of one compound ontoanother, or combinations thereof. Following a contacting method, thecontacted mixture of the support material, electron-withdrawing anion,and optional metal ion, can be calcined.

According to another embodiment of the present disclosure, the supportmaterial can be treated by a process that includes: (i) contacting asupport material with a first electron-withdrawing anion source compoundto form a first mixture; (ii) calcining the first mixture to produce acalcined first mixture; (iii) contacting the calcined first mixture witha second electron-withdrawing anion source compound to form a secondmixture; and (iv) calcining the second mixture to form the treatedsupport material.

Polymerization Processes

In at least one embodiment, the present disclosure providespolymerization processes where monomer (e.g., ethylene and/orpropylene), and optionally comonomer, are contacted with a catalystsystem containing one or more transition metal complex catalysts and oneor more activators, as described above. The catalyst compound andactivator may be combined in any order, and are combined prior tocontacting with the monomer.

In at least one embodiment, a polymerization process includes a)contacting one or more olefin monomers with a catalyst systemcontaining: i) an activator and ii) a catalyst compound. The activatormay be an alumoxane or a non-coordination anion activator. The one ormore olefin monomers can be or include, but are not limited to,ethylene, propylene, butylene, or any combination thereof. Thepolymerization process further includes heating the one or more olefinmonomers and the catalyst system to 70° C. or more to form polyethylene,polypropylene, or a copolymer containing both polyethylene andpolypropylene.

Monomers useful herein include substituted or unsubstituted C₂ to C₄₀alpha olefins, such as C₂ to C₂₀ alpha olefins, such as C₂ to C₁₂ alphaolefins, such as ethylene, propylene, butene, pentene, hexene, heptene,octene, nonene, decene, undecene, dodecene and isomers thereof. In atleast one embodiment, the monomer contains ethylene and an optionalcomonomers containing one or more ethylene or C₄ to C₄₀ olefins, such asC₄ to C₂₀ olefins, such as C₆ to C₁₂ olefins. The C₄ to C₄₀ olefinmonomers may be linear, branched, or cyclic. The C₄ to C₄₀ cyclicolefins may be strained or unstrained, monocyclic or polycyclic, and mayoptionally include heteroatoms and/or one or more functional groups. Inat least one embodiment, the monomer contains ethylene and an optionalcomonomers containing one or more C₃ to C₄₀ olefins, such as C₄ to C₂₀olefins, such as C₆ to C₁₂ olefins. The C₃ to C₄₀ olefin monomers may belinear, branched, or cyclic. The C₃ to C₄₀ cyclic olefins may bestrained or unstrained, monocyclic or polycyclic, and may optionallyinclude heteroatoms and/or one or more functional groups.

Exemplary C₂ to C₄₀ olefin monomers and optional comonomers includeethylene, propylene, butene, pentene, hexene, heptene, octene, nonene,decene, undecene, dodecene, norbornene, norbornadiene,dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene,cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene,substituted derivatives thereof, and isomers thereof, such as hexene,heptene, octene, nonene, decene, dodecene, cyclooctene,1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene,norbornadiene, and their respective homologs and derivatives, such asnorbornene, norbornadiene, and dicyclopentadiene.

In at least one embodiment, one or more dienes are present in thepolymer produced herein at up to 20 wt %, such as at about 0.00001 wt %to about 10 wt %, such as about 0.002 wt % to about 1 wt %, such asabout 0.003 wt % to about 0.2 wt %, based upon the total weight of thecomposition. In at least one embodiment, 500 ppm or less of diene isadded to the polymerization, such as 400 ppm or less, such as 300 ppm orless. In other embodiments at least 50 ppm of diene is added to thepolymerization, or 100 ppm or more, or 150 ppm or more.

Diolefin monomers include any hydrocarbon structure, such as C₄ to C₃₀,having at least two unsaturated bonds, where at least two of theunsaturated bonds are readily incorporated into a polymer by either astereospecific or a non-stereospecific catalyst(s). The diolefinmonomers can be selected from alpha, omega-diene monomers (e.g.,di-vinyl monomers). The diolefin monomers are linear di-vinyl monomers,such as those containing from 4 carbon atoms to 30 carbon atoms.Examples of dienes include butadiene, pentadiene, hexadiene, heptadiene,octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene,tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene,octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene,tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene,heptacosadiene, octacosadiene, nonacosadiene, triacontadiene,1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1,000 g/mol). Cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

Polymerization processes of the present disclosure can be carried out inany suitable manner. Any suitable suspension, homogeneous, bulk,solution, slurry, or gas phase polymerization process can be used. Suchprocesses can be run in a batch, semi-batch, or continuous mode.Homogeneous polymerization processes and slurry processes can beperformed. For example, a homogeneous polymerization process is onewhere at least 90 wt % of the product is soluble in the reaction media.A bulk homogeneous process can be used. For example, a bulk process isone where monomer concentration in all feeds to the reactor is 70 volume% or more. Alternately, no solvent or diluent is present or added in thereaction medium, (except for the small amounts used as the carrier forthe catalyst system or other additives, or amounts found with themonomer; e.g., propane in propylene). In at least one, the process is aslurry polymerization process. As used herein the term “slurrypolymerization process” means a polymerization process where a supportedcatalyst is employed and monomers are polymerized on the supportedcatalyst particles. At least 95 wt % of polymer products derived fromthe supported catalyst are in granular form as solid particles (notdissolved in the diluent).

Suitable diluents/solvents for polymerization include non-coordinating,inert liquids. Examples include straight and branched-chainhydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes,isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic andalicyclic hydrocarbons, such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane, and mixtures thereof, such as canbe found commercially (Isopar™); perhalogenated hydrocarbons, such asperfluorinated C₄-C₁₀ alkanes, chlorobenzene, and aromatic andalkylsubstituted aromatic compounds, such as benzene, toluene,mesitylene, and xylene. Suitable solvents also include liquid olefinswhich may act as monomers or comonomers including ethylene, propylene,1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,1-octene, 1-decene, and mixtures thereof. In at least one embodiment,aliphatic hydrocarbon solvents are used as the solvent, such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof. In at least one embodiment,the solvent is not aromatic, such that aromatics are present in thesolvent at less than 1 wt %, such as less than 0.5 wt %, such as lessthan 0 wt % based upon the weight of the solvents.

In at least one embodiment, the feed concentration of the monomers andcomonomers for the polymerization is 80 vol % solvent or less, 60 vol %solvent or less, such as 40 vol % or less, such as 20 vol % or less,based on the total volume of the feedstream. The polymerization can beperformed in a bulk process.

Polymerizations can be performed at any temperature and/or pressuresuitable to obtain the desired polymers, such as ethylene and orpropylene polymers. Suitable temperatures and/or pressures include atemperature in the range of from about 0° C. to about 300° C., such asabout 20° C. to about 200° C., such as about 35° C. to about 150° C.,such as about 40° C. to about 120° C., such as about 45° C. to about 80°C., for example about 80° C., and at a pressure in the range of fromabout 0.35 MPa to about 10 MPa, such as about 0.45 MPa to about 6 MPa,such as about 0.5 MPa to about 4 MPa, such as 0.66 MPa or 0.93 MPa, forexample.

In a suitable polymerization, the run time of the reaction is up to 300minutes, such as in the range of from about 5 minutes to about 250minutes, such as about 10 minutes to about 120 minutes.

In at least one embodiment, hydrogen is present in the polymerizationreactor at a partial pressure of about 0.001 psig to about 50 psig(about 0.007 kPa to about 345 kPa), such as from about 0.01 psig toabout 25 psig (about 0.07 kPa to about 172 kPa), such as about 0.1 psigto about 10 psig (about 0.7 kPa to about 70 kPa).

In at least one embodiment, the catalyst system or the transition metalcomplex has a catalytic activity of about 10 kg/mmol/hr or greater, suchas of about 20 kg/mmol/hr or greater, such as of about 40 kg/mmol/hr orgreater, such as of about 50 kg/mmol/hr or greater, such as of about 70kg/mmol/hr or greater, such as of about 80 kg/mmol/hr or greater, suchas of about 90 kg/mmol/hr or greater, such as of about 100 kg/mmol/hr orgreater, such as of about 120 kg/mmol/hr or greater, such as of about150 kg/mmol/hr or greater, such as of about 180 kg/mmol/hr or greater,such as of about 200 kg/mmol/hr or greater, such as of about 250kg/mmol/hr or greater, such as of about 300 kg/mmol/hr or greater, suchas of about 350 kg/mmol/hr or greater, such as of about 400 kg/mmol/hror greater, such as of about 450 kg/mmol/hr or greater, such as of about500 kg/mmol/hr or greater, such as of about 550 kg/mmol/hr or greater,such as of about 600 kg/mmol/hr or greater, such as of about 700kg/mmol/hr or greater, such as of about 800 kg/mmol/hr or greater, suchas of about 900 kg/mmol/hr or greater, such as of about 1,000 kg/mmol/hror greater, such as of about 1,200 kg/mmol/hr or greater, such as ofabout 1,500 kg/mmol/hr or greater, such as of about 2,000 kg/mmol/hr, orgreater. For example, the catalyst system or the transition metalcomplex has a catalytic activity of about 10 kg/mmol/hr to about 2,000kg/mmol/hr, such as about 10 kg/mmol/hr to about 1,500 kg/mmol/hr, suchas about 10 kg/mmol/hr to about 1,000 kg/mmol/hr, such as about 10kg/mmol/hr to about 800 kg/mmol/hr, such as about 10 kg/mmol/hr to about700 kg/mmol/hr, such as about 10 kg/mmol/hr to about 600 kg/mmol/hr,such as about 10 kg/mmol/hr to about 500 kg/mmol/hr, such as about 10kg/mmol/hr to about 400 kg/mmol/hr, such as about 10 kg/mmol/hr to about300 kg/mmol/hr, such as about 50 kg/mmol/hr to about 1,500 kg/mmol/hr,such as about 50 kg/mmol/hr to about 1,000 kg/mmol/hr, such as about 50kg/mmol/hr to about 800 kg/mmol/hr, such as about 50 kg/mmol/hr to about700 kg/mmol/hr, such as about 50 kg/mmol/hr to about 600 kg/mmol/hr,such as about 50 kg/mmol/hr to about 500 kg/mmol/hr, such as about 50kg/mmol/hr to about 400 kg/mmol/hr, such as about 50 kg/mmol/hr to about300 kg/mmol/hr, such as about 100 kg/mmol/hr to about 1,500 kg/mmol/hr,such as about 100 kg/mmol/hr to about 1,000 kg/mmol/hr, such as about100 kg/mmol/hr to about 800 kg/mmol/hr, such as about 100 kg/mmol/hr toabout 700 kg/mmol/hr, such as about 100 kg/mmol/hr to about 600kg/mmol/hr, such as about 100 kg/mmol/hr to about 500 kg/mmol/hr, suchas about 100 kg/mmol/hr to about 400 kg/mmol/hr, such as about 100kg/mmol/hr to about 300 kg/mmol/hr, such as about 200 kg/mmol/hr toabout 1,500 kg/mmol/hr, such as about 200 kg/mmol/hr to about 1,000kg/mmol/hr, such as about 200 kg/mmol/hr to about 800 kg/mmol/hr, suchas about 200 kg/mmol/hr to about 700 kg/mmol/hr, such as about 200kg/mmol/hr to about 600 kg/mmol/hr, such as about 200 kg/mmol/hr toabout 500 kg/mmol/hr, about 200 kg/mmol/hr to about 400 kg/mmol/hr, suchas about 200 kg/mmol/hr to about 300 kg/mmol/hr, such as about 400kg/mmol/hr to about 1,500 kg/mmol/hr, such as about 400 kg/mmol/hr toabout 1,000 kg/mmol/hr, such as about 400 kg/mmol/hr to about 800kg/mmol/hr, such as about 400 kg/mmol/hr to about 700 kg/mmol/hr, suchas about 400 kg/mmol/hr to about 600 kg/mmol/hr, such as about 400kg/mmol/hr to about 500 kg/mmol/hr, such as or about 300 kg/mmol/hr toabout 400 kg/mmol/hr.

In at least one embodiment, the catalyst system or the transition metalcomplex has a catalytic activity of in a range from about 10 kg/mmol/hrto about 1,000 kg/mmol/hr, such as about 100 kg/mmol/hr to about 1,000kg/mmol/hr, such as about 100 kg/mmol/hr to about 600 kg/mmol/hr, suchas about 200 kg/mmol/hr to about 600 kg/mmol/hr, such as about 400kg/mmol/hr to about 600 kg/mmol/hr.

In at least one embodiment, the conversion of olefin monomer is at least10%, based upon polymer yield and the weight of the monomer entering thereaction zone, such as 20% or more, such as 30% or more, such as 50% ormore, such as 80% or more. In at least one embodiment, a catalyst of thepresent disclosure has an activity of 25,000 g/mmol/hr to about 260,000g/mmol/hr. In at least one embodiment, a catalyst of the presentdisclosure is capable of producing polyethylene having an Mw from about40,000 g/mol to about 1,500,000 g/mol, such as from about 180,000 g/molto about 1,000,000 g/mol, such as from about 300,000 g/mol to about900,000 g/mol, such as from about 400,000 g/mol to about 800,000 g/mol,such as from about 500,000 g/mol to about 660,000 g/mol. In at least oneembodiment, a catalyst of the present disclosure is capable of producingpolyethylene having an Mn from about 30,000 g/mol to about 1,000,000g/mol, such as from about 70,000 g/mol to about 500,000 g/mol, such asfrom about 100,000 g/mol to about 400,000 g/mol, such as from about250,000 g/mol to about 300,000 g/mol. In at least one embodiment, acatalyst of the present disclosure is capable of producing polyethylenehaving an Mw/Mn value from about 1 to about 5, such as from about 1.5 toabout 4, such as from about 2 to about 4, such as from about 2.5 toabout 3.5. In at least one embodiment, for catalyst systems containingand one or more transition metal complex catalysts, such as a catalystof Formulas (II), (V), (VI) and (VII), a polyethylene formed by thecatalyst system have an Mw/Mn value from about 1 to about 5, such asfrom about 1.5 to about 4, such as from about 2 to about 4, such as fromabout 2.5 to about 3.5. In at least one embodiment, a catalyst of thepresent disclosure is capable of producing polyethylene having acomonomer content C₈ wt % of 10 wt % or greater, such as 12 wt % orgreater, such as 15 wt % or greater, such as 17 wt % or greater, such as19 wt % or greater, such as 19.5 wt %, for example.

In at least one embodiment, little or no alumoxane is used in theprocess to produce the polymers. Alumoxane can be present at zero mol %,alternatively the alumoxane is present at a molar ratio of aluminum totransition metal less than 500:1, such as less than 300:1, such as lessthan 100:1, such as less than 1:1.

In at least one embodiment, little or no scavenger is used in theprocess to produce the ethylene polymer. Scavenger (such as trialkylaluminum) can be present at zero mol %, alternately the scavenger ispresent at a molar ratio of scavenger metal to transition metal of lessthan 100:1, such as less than 50:1, such as less than 15:1, such as lessthan 10:1.

In at least one embodiment, the polymerization: 1) is conducted attemperatures of about 0° C. to about 300° C. (such as about 25° C. toabout 150° C., such as about 40° C. to about 120° C., such as about 70°C. to about 110° C.); 2) is conducted at a pressure of atmosphericpressure to 10 MPa (such as about 0.35 MPa to about 10 MPa, such as fromabout 0.45 MPa to about 6 MPa, such as from about 0.5 MPa to about 4MPa); 3) is conducted in an aliphatic hydrocarbon solvent (such asisobutane, butane, pentane, isopentane, hexanes, isohexane, heptane,octane, dodecane, and mixtures thereof; cyclic and alicyclichydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane,methylcycloheptane, and mixtures thereof, where aromatics are present inthe solvent at less than 1 wt %, such as less than 0.5 wt %, such as at0 wt % based upon the weight of the solvents); and 4) the activity ofthe catalyst compound is at least 25,000 g/mmol/hr, such about 150,000g/mmol/hr, about 200,000 g/mmol/hr, about 250,000 g/mmol/hr or greater.In at least one embodiment, the catalyst system used in thepolymerization includes no more than one catalyst compound. A “reactionzone” also referred to as a “polymerization zone” is a vessel wherepolymerization takes place, for example a batch reactor. When multiplereactors are used in either series or parallel configuration, eachreactor is considered as a separate polymerization zone. For amulti-stage polymerization in both a batch reactor and a continuousreactor, each polymerization stage is considered as a separatepolymerization zone. In at least one embodiment, the polymerizationoccurs in one reaction zone.

Other additives may also be used in the polymerization, as desired, suchas one or more scavengers, promoters, modifiers, chain transfer agents(such as diethyl zinc), reducing agents, oxidizing agents, hydrogen,aluminum alkyls, or silanes.

Chain Transfer Agent

A “chain transfer agent” (CTA) is any agent capable of hydrocarbyland/or polymeryl group exchange between a coordinative polymerizationcatalyst and the metal center of the chain transfer agent during apolymerization process. The chain transfer agent can be any desirablechemical compound such as those disclosed in WO 2007/130306. The chaintransfer agent can be selected from Group 2, 12, or 13 alkyl or arylcompounds, such as zinc, magnesium, or aluminum alkyls or aryls. In someexamples, the alkyl is a C₁-C₃₀ alkyl, a C₂-C₂₀ alkyl, or a C₃-C₁₂alkyl. Suitable alkyls for the CTA can be or include, but are notlimited to, methyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl,hexyl, cyclohexyl, phenyl, octyl, nonyl, decyl, undecyl, dodecyl,isomers thereof, or any combination thereof.

In at least one embodiment, the chain transfer agent is selected fromdialkyl zinc compounds, where the alkyl is independently selected frommethyl, ethyl, propyl, butyl, isobutyl, tertbutyl, pentyl, hexyl,cyclohexyl, and phenyl. In at least one embodiment, the chain transferagent is selected from trialkyl aluminum compounds, where the alkyl isindependently selected from methyl, ethyl, propyl, butyl, isobutyl,tertbutyl, pentyl, hexyl, and cyclohexyl. In at least one embodiment,the chain transfer agent is selected from tri aryl aluminum compoundswhere the aryl is selected from phenyl and substituted phenyl.

In at least one embodiment, the process is characterized by the transferof at least 0.5 polymer chains (e.g., 0.5 to 3) polymer chains, where nis the maximum number of polymer chains that can be transferred to thechain transfer agent metal, such as n is 1 to 3 for trivalent metals(such as Al) and 1 to 2 for divalent metals (such as Zn), such as n is1.5 to 3 for trivalent metals (such as Al) and 1.5-2 for divalent metals(such as Zn). The number of chains transferred per metal is the slope ofthe plot of moles of polymer produced versus the moles of the chaintransfer agent metal (as determined from at least four points, CTAmetal:catalyst transition metal of 20:1, 80:1, 140:1 and 200:1, usingleast squares fit (Microsoft™ Excel 2010, version 14.0.7113.5000 (32bit)) to draw the line.

Suitable chain transfer agents can be present at from 10 or 20 or 50 or100 equivalents to 600 or 700 or 800 or 1,000 or 2,000 or 4,000equivalents relative to the catalyst component. Alternately the chaintransfer agent is preset at a catalyst complex-to-CTA molar ratio offrom about 1:12,000 to 10:1; alternatively 1:6,000; alternatively,1:3,000 to 10:1; alternatively 1:2,000 to 10:1; alternatively 1:1,000 to10:1; alternatively, 1:500 to 1:1; alternatively 1:300 to 1:1;alternatively 1:200 to 1:1; alternatively 1:100 to 1:1; alternatively1:50 to 1:1; alternatively 1:10 to 1:1.

Suitable chain transfer agents can be or include a compound representedby the formula AlR₃, MgR₂, or ZnR₂, where each R is, independently, aC₁-C₈ hydrocarbyl, such as methyl, ethyl, propyl, butyl, phenyl, hexyl,octyl, or an isomer thereof. Suitable chain transfer agents can be orinclude, but are not limited to, diethylzinc, tri-n-octyl aluminum,trimethylaluminum, triethylaluminum, tri-isobutylaluminum,tri-n-hexylaluminum, trioctylaluminum, diethyl aluminum chloride, methylalumoxane, dibutyl zinc, di-n-propylzinc, di-n-hexylzinc,di-n-pentylzinc, di-n-decylzinc, di-n-dodecylzinc, di-n-tetradecylzinc,di-n-hexadecylzinc, di-n-octadecylzinc, diphenylzinc, diisobutylaluminumhydride, diethylaluminum hydride, di-n-octylaluminum hydride,dibutylmagnesium, diethylmagnesium, dihexylmagnesium, triethylboron, orany combination thereof.

In at least one embodiment, two or more complexes are combined withdiethyl zinc and/or tri-n-octylaluminum in the same reactor withmonomer(s). Alternately, one or more complexes is/are combined withanother catalyst and diethyl zinc and/or tri-n-octylaluminum in the samereactor with monomers.

In at least one embodiment, one or more complexes is/are combined with amixture of diethyl zinc and an aluminum reagent in the same reactor withmonomer(s). Alternately, one or more complexes is/are combined with twochain transfer agents in the same reactor with monomers.

Polyolefin Products

The present disclosure also provides compositions of matter which can beproduced by the methods described herein.

In at least one embodiment, the process described herein producesethylene homopolymers or ethylene copolymers, such as ethylene-propyleneand/or ethylene-alpha-olefin (such as C₄ to C₂₀) copolymers (such asethylene-hexene copolymers or ethylene-octene copolymers) having anMw/Mn of greater than 1 to 4 (such as greater than 1 to 3).

Likewise, the process of the present disclosure produces olefinpolymers, such as polyethylene and polypropylene homopolymers andcopolymers. In at least one embodiment, the polymers produced herein arehomopolymers of ethylene or propylene, are copolymers of ethylene suchas copolymer of ethylene having from 0 mol % to about 25 mol % (such asfrom about 0.5 mol % to about 20 mol %, such as from about 1 mol % toabout 15 mol %, such as from about 3 mol % to about 10 mol %) of one ormore C₃ to C₂₀ olefin comonomer (such as C₃ to C₁₂ alpha-olefin, such aspropylene, butene, hexene, octene, decene, dodecene, such as propylene,butene, hexene, octene), or are copolymers of propylene such ascopolymers of propylene having from 0 mol % to about 25 mol % (such asfrom about 0.5 mol % to about 20 mol %, such as from about 1 mol % toabout 15 mol %, such as from about 3 mol % to about 10 mol %) of one ormore of C₂ or C₄ to C₂₀ olefin comonomer (such as ethylene or C₄ to C₁₂alpha-olefin, such as butene, hexene, octene, decene, dodecene, such asethylene, butene, hexene, octene).

In at least one embodiment, a polymer, such as polyethylene, has acomonomer content of 10 wt % or greater, such as 12 wt % or greater,such as 15 wt % or greater, such as 17 wt % or greater, such as 19 wt %or greater, such as 19.5 wt %, for example. In at least one embodiment,the monomer is ethylene and the comonomer is octene, such as from about10 wt % to about 20 wt % octene, such as about 12 wt % to about 19.5 wt% octene.

In at least one embodiment, a polymer, such as polyethylene, has a Tmfrom about 80° C. to about 115° C., such as from about 82° C. to about110° C., such as from about 85° C. to about 105° C., as determined byDifferential Scanning calorimetry. For purposes of the claims to thisinvention the following DSC procedure shall be used:

Differential Scanning calorimetry. Melting Temperature, Tm, is measuredby differential scanning calorimetry (“DSC”) using a DSCQ200 unit. Thesample is first equilibrated at 25° C. and subsequently heated to 220°C. using a heating rate of 10° C./min (first heat). The sample is heldat 220° C. for 3 minutes. The sample is subsequently cooled down to−100° C. with a constant cooling rate of 10° C./min (first cool). Thesample is equilibrated at −100° C. before being heated to 220° C. at aconstant heating rate of 10° C./min (second heat). The exothermic peakof crystallization (first cool) is analyzed using the TA UniversalAnalysis software and the corresponding to 10° C./min cooling rate isdetermined. The endothermic peak of melting (second heat) is alsoanalyzed using the TA Universal Analysis software and the peak meltingtemperature (Tm) corresponding to 10° C./min heating rate is determined.

In at least one embodiment, a polymer, such as polyethylene, has an Mwfrom about 40,000 g/mol to about 1,500,000 g/mol, such as from about180,000 g/mol to about 1,000,000 g/mol, such as from about 300,000 g/molto about 900,000 g/mol, such as from about 400,000 g/mol to about800,000 g/mol, such as from about 500,000 g/mol to about 660,000 g/mol.In at least one embodiment, a polymer, such as polyethylene, has an Mnfrom about 30,000 g/mol to about 1,000,000 g/mol, such as from about70,000 g/mol to about 500,000 g/mol, such as from about 100,000 g/mol toabout 400,000 g/mol, such as from about 200,000 g/mol to about 400,000g/mol. In at least one embodiment, a polymer, such as polyethylene, hasan Mw/Mn value from about 1 to about 5, such as from about 1.1 to about4, such as from about 1.2 to about 3, such as from about 1.4 to about2.5.

Molecular Weight, Comonomer Composition and Long Chain BranchingDetermination by Polymer Char GPC-IR Hyphenated with Multiple Detectors

For purposes of the claims, and unless otherwise indicated, thedistribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn,etc.), the comonomer content (C₂, C₃, C₆, etc.) are determined by usinga high temperature Gel Permeation Chromatography

(Polymer Char GPC-IR) equipped with a multiple-channel band-filter basedInfrared detector IR5, an 18-angle light scattering detector and aviscometer. Three Agilent PLgel 10-μm Mixed-B LS columns are used toprovide polymer separation. Aldrich reagent grade 1,2,4-trichlorobenzene(TCB) with 300 ppm antioxidant butylated hydroxytoluene (BHT) is used asthe mobile phase. The TCB mixture is filtered through a 0.1-μm Teflonfilter and degassed with an online degasser before entering the GPCinstrument. The nominal flow rate is 1.0 ml/min and the nominalinjection volume is 200 μL. The whole system including transfer lines,columns, and detectors are contained in an oven maintained at 145° C.Given amount of polymer sample is weighed and sealed in a standard vialwith 80-4 flow marker (Heptane) added to it. After loading the vial inthe autosampler, polymer is automatically dissolved in the instrumentwith 8 ml added TCB solvent. The polymer is dissolved at 160° C. withcontinuous shaking for about 1 hour for most polyethylene samples or 2hours for polypropylene samples. The TCB densities used in concentrationcalculation are 1.463 g/ml at room temperature and 1.284 g/ml at 145° C.The sample solution concentration is from 0.2 to 2.0 mg/ml, with lowerconcentrations being used for higher molecular weight samples. Theconcentration (c), at each point in the chromatogram is calculated fromthe baseline-subtracted IR5 broadband signal intensity (I), using thefollowing equation: c=βI, where β is the mass constant. The massrecovery is calculated from the ratio of the integrated area of theconcentration chromatography over elution volume and the injection masswhich is equal to the pre-determined concentration multiplied byinjection loop volume. The conventional molecular weight (IR MW) isdetermined by combining universal calibration relationship with thecolumn calibration which is performed with a series of monodispersedpolystyrene (PS) standards ranging from 700 to 10M gm/mole. The MW ateach elution volume is calculated with following equation:

${\log \; M} = {\frac{\log \left( {K_{PS}/K} \right)}{\alpha + 1} + {\frac{\alpha_{PS} + 1}{\alpha + 1}\log \; M_{PS}}}$

where the variables with subscript “PS” stand for polystyrene whilethose without a subscript are for the test samples. In this method,α_(PS)=0.67 and K_(PS)=0.000175, while a and K for other materials areas calculated and published in literature (Sun, T. et al. (2001)Macromolecules, v. 34(19), pp. 6812-6820), except that for purposes ofthis invention and claims thereto, α=0.695+(0.01*(wt. fractionpropylene)) and K=0.000579-(0.0003502*(wt. fraction propylene)) forethylene-propylene copolymers and ethylene-propylene-diene terpolymers,α=0.695 and K=0.000579 for linear ethylene polymers, α=0.705 andK=0.0002288 for linear propylene polymers, α=0.695 and K=0.000181 forlinear butene polymers, α is 0.695 and K is0.000579*(1-0.0087*w2b+0.000018*(w2b)−2) for ethylene-butene copolymerwhere w2b is a bulk weight percent of butene comonomer, a is 0.695 and Kis 0.000579*(1-0.0075*w2b) for ethylene-hexene copolymer where w2b is abulk weight percent of hexene comonomer, and α is 0.695 and K is0.000579*(1-0.0077*w2b) for ethylene-octene copolymer where w2b is abulk weight percent of octene comonomer. Concentrations are expressed ing/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity(hence K in the Mark-Houwink equation) is expressed in dL/g unlessotherwise noted.

The comonomer composition is determined by the ratio of the IR5 detectorintensity corresponding to CH₂ and CH₃ channel calibrated with a seriesof PE and PP homo/copolymer standards whose nominal value arepredetermined by NMR or FTIR. In particular, this provides the methylsper 1,000 total carbons (CH₃/1000TC) as a function of molecular weight.The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is thencomputed as a function of molecular weight by applying a chain-endcorrection to the CH₃/1000TC function, assuming each chain to be linearand terminated by a methyl group at each end. The weight % comonomer isthen obtained from the following expression in which f is 0.3, 0.4, 0.6,0.8, and so on for C₃, C₄, C₆, C₈, and so on co-monomers, respectively:

w2=f*SCB/1000TC.

The bulk composition of the polymer from the GPC-IR and GPC-4D analysesis obtained by considering the entire signals of the CH₃ and CH₂channels between the integration limits of the concentrationchromatogram. First, the following ratio is obtained

${{Bulk}\mspace{14mu} {IR}\mspace{14mu} {ratio}} = {\frac{{Area}\mspace{14mu} {of}\mspace{14mu} {CH}_{3}\mspace{14mu} {signal}\mspace{14mu} {within}\mspace{14mu} {integration}\mspace{14mu} {limits}}{{Area}\mspace{14mu} {of}\mspace{14mu} {CH}_{2}\mspace{14mu} {signal}\mspace{14mu} {within}\mspace{14mu} {integration}\mspace{14mu} {limits}}.}$

Then the same calibration of the CH₃ and CH₂ signal ratio, as mentionedpreviously in obtaining the CH3/1000TC as a function of molecularweight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chainends per 1000TC (bulk CH3end/1000TC) is obtained by weight-averaging thechain-end correction over the molecular-weight range. Then

w2b=f*bulk CH3/1000TC

bulk SCB/1000TC=bulk CH3/1000TC−bulk CH3end/1000TC

and bulk SCB/1000TC is converted to bulk w2 in the same manner asdescribed above.

The LS detector is the 18-angle Wyatt Technology High Temperature DAWNHELEOSII. The LS molecular weight (M) at each point in the chromatogramis determined by analyzing the LS output using the Zimm model for staticlight scattering (Light Scattering from Polymer Solutions; Huglin, M.B., Ed.; Academic Press, 1972.):

$\frac{K_{o}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2\; A_{2}{c.}}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theIR5 analysis, A2 is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil, and K_(O) is the optical constantfor the system:

$K_{o} = \frac{4\; \pi^{2}{n^{2}\left( {{{dn}/d}\; c} \right)}^{2}}{\lambda^{4}N_{A}}$

where N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 145°C. and λ=665 nm. For analyzing ethylene homopolymers, ethylene-hexenecopolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg andA₂=0.0015; for analyzing ethylene-butene copolymers,dn/dc=0.1048*(1−0.00126*w2) ml/mg and A₂=0.0015 where w2 is weightpercent butene comonomer.

In at least one embodiment, the polymer produced herein has a unimodalor multimodal molecular weight distribution as determined by GelPermeation Chromatography (GPC). By “unimodal” is meant that the GPCtrace has one peak or inflection point. By “multimodal” is meant thatthe GPC trace has at least two peaks or inflection points. An inflectionpoint is that point where the second derivative of the curve changes insign (e.g., from negative to positive or vice versus).

In at least one embodiment, a bimodal polymer, such as a bimodalpolyethylene (e.g., formed by a catalyst system having a catalystrepresented by Formulas (II), (V), (VI) and (VII) and another type ofcatalyst, such as, for example, a metallocene catalyst) has an Mw/Mnvalue from about 1 to about 10, such as from about 1.5 to about 8, suchas from about 2 to about 4, such as from about 2 to about 3.

In at least one embodiment, the polymer produced herein has acomposition distribution breadth index (CDBI) of 50% or more, such as60% or more, such as 70% or more. CDBI is a measure of the compositiondistribution of monomer within the polymer chains and is measured by theprocedure described in PCT publication WO 1993/003093, published Feb.18, 1993, specifically columns 7 and 8 as well as in Wild, L. et al.(1982) J. Poly. Sci., Poly. Phys. Ed., v 20, pp. 441-455 and U.S. Pat.No. 5,008,204, including that fractions having a weight averagemolecular weight (Mw) below 15,000 are ignored when determining CDBI.

Blends

In at least one embodiment, the polymer (such as polyethylene orpolypropylene) produced herein is combined with one or more additionalpolymers prior to being formed into a film, molded part or otherarticle. Other useful polymers include polyethylene, isotacticpolypropylene, highly isotactic polypropylene, syndiotacticpolypropylene, LDPE, LLDPE, HDPE, random copolymer of ethylene andpropylene, and/or butene, hexene, polybutene, ethylene vinyl acetate,ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylicacid, polymethylmethacrylate or any other polymers polymerizable by ahigh-pressure free radical process, polyvinylchloride, polybutene-1,isotactic polybutene, ABS resins, ethylene-propylene rubber (EPR),vulcanized EPR, EPDM, block copolymer, styrenic block copolymers,polyamides, polycarbonates, PET resins, cross linked polyethylene,copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromaticmonomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidinefluoride, polyethylene glycols, and/or polyisobutylene.

In at least one embodiment, the polymer (such as polyethylene orpolypropylene) is present in the above blends, at from 10 to 99 wt %,based upon the weight of the polymers in the blend, such as 20 to 95 wt%, such as at least 30 to 90 wt %, such as at least 40 to 90 wt %, suchas at least 50 to 90 wt %, such as at least 60 to 90 wt %, such as atleast 70 to 90 wt %.

The blends described above may be produced by mixing the polymers of thepresent disclosure with one or more polymers (as described above), byconnecting reactors together in series to make reactor blends or byusing more than one catalyst in the same reactor to produce multiplespecies of polymer. The polymers can be mixed together prior to beingput into the extruder or may be mixed in an extruder.

The blends may be formed using conventional equipment and methods, suchas by dry blending the individual components and subsequently meltmixing in a mixer, or by mixing the components together directly in amixer, such as, for example, a Banbury mixer, a Haake mixer, a Brabenderinternal mixer, or a single or twin-screw extruder, which may include acompounding extruder and a side-arm extruder used directly downstream ofa polymerization process, which may include blending powders or pelletsof the resins at the hopper of the film extruder. Additionally,additives may be included in the blend, in one or more components of theblend, and/or in a product formed from the blend, such as a film, asdesired. Such additives are well known in the art, and can include, forexample: fillers; antioxidants (e.g., hindered phenolics such asIRGANOX™ 1010 or IRGANOX™ 1076 available from Ciba-Geigy); phosphites(e.g., IRGAFOS™ 168 available from Ciba-Geigy); anti-cling additives;tackifiers, such as polybutenes, terpene resins, aliphatic and aromatichydrocarbon resins, alkali metal and glycerol stearates, andhydrogenated rosins; UV stabilizers; heat stabilizers; anti-blockingagents; release agents; anti-static agents; pigments; colorants; dyes;waxes; silica; fillers; talc; and the like.

Films

Specifically, any of the foregoing polymers, such as the foregoingpolyethylenes or blends thereof, may be used in a variety of end-useapplications. Such applications include, for example, mono- ormulti-layer blown, extruded, and/or shrink films. These films may beformed by any number of extrusion or coextrusion techniques, such as ablown bubble film processing technique, wherein the composition can beextruded in a molten state through an annular die and then expanded toform a uni-axial or biaxial orientation melt prior to being cooled toform a tubular, blown film, which can then be axially slit and unfoldedto form a flat film. Films may be subsequently unoriented, uniaxiallyoriented, or biaxially oriented to the same or different extents. One ormore of the layers of the film may be oriented in the transverse and/orlongitudinal directions to the same or different extents. The uniaxialorientation can be accomplished using cold drawing or hot drawingmethods. Biaxial orientation can be accomplished using tenter frameequipment or a double bubble processes and may occur before or after theindividual layers are brought together. For example, a polyethylenelayer can be extrusion coated or laminated onto an orientedpolypropylene layer or the polyethylene and polypropylene can becoextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. For example, the films areoriented in the Machine Direction (MD) at a ratio of up to 15, such asbetween 5 and 7, and in the Transverse Direction (TD) at a ratio of upto 15, such as 7 to 9. However, in at least one embodiment the film isoriented to the same extent in both the MD and TD directions.

The films may vary in thickness depending on the intended application;however, films of a thickness from 1 to 50 μm are usually suitable.Films intended for packaging are usually from 10 to 50 μm thick.Suitable thickness of the sealing layer can be 0.2 μm to 50 μm. Theremay be a sealing layer on both the inner and outer surfaces of the filmor the sealing layer may be present on only the inner or the outersurface.

In at least one embodiment, one or more layers is modified by coronatreatment, electron beam irradiation, gamma irradiation, flametreatment, or microwave. In at least one embodiment, one or both of thesurface layers is modified by corona treatment.

This invention also relates to:

1. A ligand represented by Formula (I):

wherein:

Q¹ is a Group 15 atom;

Q² is a Group 15 atom or a Group 16 atom, wherein n is 0 if Q² is aGroup 16 atom or n is 1 if Q² is a Group 15 atom;

R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl;

each R² is independently a hydrogen, a substituted or unsubstitutedlinear, branched, cyclic, polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, ora heteroatom-containing group; and

each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently a hydrogen, ahalogen, a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R³-R¹⁰ groups are joined together to forma C₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group;

L¹ is

and is not part of an aromatic ring;

L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10;

each instance of R¹¹ is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and

each instance of R¹² is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.

2. A catalyst compound represented by Formula (II):

wherein:

M is a Group 4 transition metal;

each X¹ and X² is independently a substituted or unsubstituted linear,branched, cyclic, polycyclic, or aromatic hydrocarbyl; or X¹ and X² arejoined together to form a C₄-C₆₂ cyclic, polycyclic, heterocyclic, oraromatic group;

Q¹ is a Group 15 atom;

Q² is a Group 15 atom or a Group 16 atom, wherein n is 0 if Q² is aGroup 16 atom or n is 1 if Q² is a Group 15 atom;

R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl;

each R² is independently a hydrogen, a substituted or unsubstitutedlinear, branched, cyclic, polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, ora heteroatom-containing group; and

each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently a hydrogen, ahalogen, a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R³-R¹⁰ groups are joined together to forma C₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group;

L¹ is

and is not part of an aromatic ring;

L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10;

each instance of R¹¹ is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and

each instance of R¹² is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.

3. The catalyst compound of paragraph 2, wherein M is Hf or Zr.4. The catalyst compound of paragraphs 2 or 3, wherein each X¹ and X² isindependently a substituted or unsubstituted C₁-C₂₀ hydrocarbyl.5. The catalyst compound of any of paragraphs 2 to 4, wherein each X¹and X² is independently a substituted or unsubstituted C₁-C₈ alkyl,phenyl, benzyl, naphthyl, or cyclohexyl.6. The catalyst compound of any of paragraphs 2 to 5, wherein each X¹and X² is benzyl.7. The catalyst compound or ligand of any of paragraphs 1 to 6, whereinR¹ is a substituted or unsubstituted C₁-C₁₀ diyl.8. The catalyst compound or ligand of any of paragraphs 1 to 6, whereinR¹ is selected from methanediyl, ethanediyl, propanediyl, butanediyl,pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl,decanediyl, undecanediyl, dodecanediyl, isomers thereof, halidesubstitutes thereof, or other substitutes thereof9. The catalyst compound or ligand of paragraph 8, wherein R¹ isselected from unsubstituted methanediyl, ethanediyl, propanediyl,butanediyl, or pentanediyl.10. The catalyst compound or ligand of any of paragraphs 1 to 9, whereinL¹ is a substituted or unsubstituted methanediyl and L² is a substitutedor unsubstituted ethanediyl, preferably, L¹ is an unsubstitutedmethanediyl and L² is an unsubstituted ethanediyl.11. The catalyst compound or ligand of any of paragraphs 1 to 10,wherein Q² is N, n is 2, and each R² is independently hydrogen orunsubstituted C₁-C₁₀ hydrocarbyl.12. The catalyst compound or ligand of paragraph 11, wherein each R² isindependently methyl or ethyl.13. The catalyst compound or ligand of any of paragraphs 1 to 12,wherein each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independentlyhydrogen, halogen, methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl,anthracenyl, carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl,imidazolyl, indenyl, indanyl, isomers thereof, halide substitutesthereof, or other substitutes thereof.14. The catalyst compound or ligand of paragraph 13, wherein each of R⁶and R¹⁰ is independently halogen, phenyl, carbazolyl, fluorenyl,adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl, orsubstitutes thereof.15. The catalyst compound of paragraph 14, wherein R⁶ is carbazolyl orfluorenyl and R¹⁰ is halogen, phenyl, carbazolyl, or fluorenyl.16. The catalyst compound or ligand of any of paragraphs 1 to 15,wherein R⁴ and R⁸ is independently substituted or unsubstituted linearor branched C₁-C₄ hydrocarbyl.17. The catalyst compound or ligand of any of paragraphs 1 to 16,wherein Q¹ and Q² are N.18. The ligand of paragraph 1, wherein the ligand is selected from anyof the ligands represented by the formulas 1 to 16 as described above.19. The catalyst compound of paragraph 2, wherein the catalyst compoundis selected from:

20. The catalyst compound of paragraph 19, wherein the catalyst compoundis selected from:

21. A catalyst system comprising an activator and the catalyst compoundof any of paragraphs 2-20.22. The catalyst system of paragraph 21, further comprising a supportmaterial.23. The catalyst system of paragraph 22, wherein the support material isselected from Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay,silicon oxide/clay, or mixtures thereof.24. The catalyst system of any of paragraphs 21-23, wherein theactivator comprises an alkylalumoxane.25. A process for the production of an ethylene alpha-olefin copolymercomprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefinby contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin witha catalyst system of paragraphs 21 to 24 in at least one solutionpolymerization reactor at a reactor pressure of from 2 MPa to 200 MPaand a reactor temperature of from 10° C. to 250° C. to form an ethylenealpha-olefin copolymer.26. The process of paragraph 25, wherein the catalyst has an activity of100,000 g/mmol/hr or greater.27. The process of paragraphs 25 or 26, wherein the ethylenealpha-olefin copolymer has an Mw value of from 250,000 to 700,000 g/mol.28. The process of any of paragraphs 25 to 27, wherein the ethylenealpha-olefin copolymer has an Mw/Mn value of 5 or less.29. The process of paragraph 28, wherein the ethylene alpha-olefincopolymer has an Mw/Mn value of from 1 to 2.30. The process of any of paragraphs 25 to 29, wherein the ethylenealpha-olefin copolymer has a comonomer content of 12 wt % or greater.31. The process of paragraph 32, wherein the ethylene alpha-olefincopolymer has a comonomer content of 15 wt % or greater.32. The process of paragraph 31, wherein the ethylene alpha-olefincopolymer has a comonomer content of 17 wt % or greater.33. An ethylene alpha-olefin copolymer comprising: ethylene; and atleast one C₃-C₂₀ alpha-olefin, wherein the copolymer has an Mw value offrom 250,000 to 700,000 g/mol, an Mw/Mn value of 5 or less, and acomonomer content of 12 wt % or greater.34. The copolymer of paragraph 33, wherein the alpha-olefin is octene.35. The copolymer of paragraphs 33 or 34, wherein the copolymer has anMw/Mn value of from 1 to 2.36. The copolymer of any of paragraphs 33 to 35, wherein the copolymerhas a comonomer content of 15 wt % or greater.37. The copolymer of any of paragraphs 33 to 36, wherein the copolymerhas a comonomer content of 17 wt % or greater.

This invention further relates to:

1A. A catalyst compound represented by Formula (II):

wherein:

M is a Group 4 transition metal, preferably Hf or Zr;

each X¹ and X² is independently a substituted or unsubstituted linear,branched, cyclic, polycyclic, or aromatic hydrocarbyl; or X¹ and X² arejoined together to form a C₄-C₆₂ cyclic, polycyclic, heterocyclic, oraromatic group;

Q¹ is a Group 15 atom;

Q² is a Group 15 atom or a Group 16 atom, wherein n is 0 if Q² is aGroup 16 atom or n is 1 if Q² is a Group 15 atom;

R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl;

each R² is independently a hydrogen, a substituted or unsubstitutedlinear, branched, cyclic, polycyclic, or aromatic hydrocarbyl, or aheteroatom-containing group; and

each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently a hydrogen, ahalogen, a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic hydrocarbyl, or a heteroatom-containing group;or two or more adjacent R³-R¹⁰ groups are joined together to form aC₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group;

L¹ is

and is not part of an aromatic ring;

L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10;

each instance of R¹¹ is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and

each instance of R¹² is independently a hydrogen, a halogen, asubstituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.

2A. The catalyst compound of paragraph 1A, wherein each X¹ and X² isindependently a substituted or unsubstituted C₁-C₈ alkyl, phenyl,benzyl, naphthyl, or cyclohexyl.3A. The catalyst compound of paragraph 1A, wherein R¹ is a substitutedor unsubstituted C₁-C₁₀ diyl, preferably R¹ is selected frommethanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl,hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl,undecanediyl, dodecanediyl, isomers thereof, halide substitutes thereof,or other substitutes thereof, preferably R¹ is selected fromunsubstituted methanediyl, ethanediyl, propanediyl, butanediyl, orpentanediyl.4A. The catalyst paragraph 1A, wherein L¹ is an unsubstitutedmethanediyl and L² is an unsubstituted ethanediyl.5A. The catalyst compound of paragraph 1A, wherein Q² is N, n is 2, andeach R² is independently hydrogen or unsubstituted C₁-C₁₀ hydrocarbyl,preferably each R² is independently methyl or ethyl.6A. The catalyst compound of paragraph 1A, wherein each R³, R⁴, R⁵, R⁶,R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, halogen, methyl, ethyl,ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl, cyclooctyl,phenyl, benzyl, naphthyl, phenanthryl, anthracenyl, carbazolyl,fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl, indenyl, indanyl,isomers thereof, halide substitutes thereof, or other substitutesthereof, preferably each of R⁶ and R¹⁰ is independently halogen, phenyl,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof.7A. The catalyst compound of paragraph 1A, wherein R⁴ and R⁸ isindependently substituted or unsubstituted linear or branched C₁-C₄hydrocarbyl.8A. The catalyst compound of paragraph 1A, wherein Q¹ and Q² are N.9A. The catalyst compound of paragraph 1A, wherein M is Hf or Zr; X¹ andX² is independently a substituted or unsubstituted C₁-C₈ alkyl, phenyl,benzyl, naphthyl, or cyclohexyl, and R¹ is a substituted orunsubstituted diyl.10A. The catalyst compound of paragraph 1A, wherein M is Hf or Zr; X¹and X² is independently a substituted or unsubstituted C₁-C₈ alkyl,phenyl, benzyl, naphthyl, or cyclohexyl, and R¹ is selected frommethanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl,hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl,undecanediyl, dodecanediyl, isomers thereof, halide substitutes thereof,or other substitutes thereof.11A. The catalyst compound of paragraph 1A, wherein R¹ is selected fromunsubstituted methanediyl, ethanediyl, propanediyl, butanediyl, orpentanediyl, and L¹ is an unsubstituted methanediyl and L² is anunsubstituted ethanediyl.12A. The catalyst compound of paragraph 1A, wherein M is Hf or Zr; X¹and X² is independently a substituted or unsubstituted C₁-C₈ alkyl,phenyl, benzyl, naphthyl, or cyclohexyl; R¹ is selected frommethanediyl, ethanediyl, propanediyl, butanediyl, pentanediyl,hexanediyl, heptanediyl, octanediyl, nonanediyl, decanediyl,undecanediyl, dodecanediyl, isomers thereof, halide substitutes thereof,or other substitutes thereof; each R² is independently hydrogen orunsubstituted hydrocarbyl; R⁶ is carbazolyl or fluorenyl; R¹⁰ ishalogen, phenyl, carbazolyl, or fluorenyl; R⁴ and R⁸ is independentlysubstituted or unsubstituted linear or branched C₁-C₄ hydrocarbyl; andQ¹ and Q² are N.13A. The catalyst compound of paragraph 1A, wherein the catalystcompound is selected from catalyst compounds 1 to 32, preferablycatalyst compounds 1 and 2 as described above.14A. A catalyst system comprising an activator, the catalyst compound ofany of paragraphs 1A to 13A, and an optional support material.15A. The catalyst system of paragraph 14A, wherein the activatorcomprises an alkylalumoxane or an non-coordinating anion.16A. A process for the production of an ethylene alpha-olefin copolymercomprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefinby contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin witha catalyst system of paragraphs 14A or 15A in at least one solutionpolymerization reactor at a reactor pressure of from 2 MPa to 200 MPaand a reactor temperature of from 10° C. to 250° C. to form an ethylenealpha-olefin copolymer, wherein the catalyst preferably has an activityof 100,000 g/mmol/hr or greater.17A. The process of paragraph 16A, wherein the ethylene alpha-olefincopolymer has an Mw value of from 250,000 to 700,000 g/mol and/or anMw/Mn value of 5 or less, preferably from 1 to 2.18A. The process of paragraph 16A or 17A, wherein the ethylenealpha-olefin copolymer has a comonomer content of 12 wt % or greater,preferably of 15 wt % or greater, preferably of 17 wt % or greater.19A. An ethylene alpha-olefin copolymer comprising: ethylene and atleast one C₃-C₂₀ alpha-olefin (preferably octene), wherein the copolymerhas an Mw value of from 250,000 to 700,000 g/mol, an Mw/Mn value of 5 orless (preferably 1 to 2), and a comonomer content of 12 wt % or greater,preferably of 15 wt % or greater, preferably of 17 wt % or greater.20A. A ligand represented by Formula (I):

wherein: Q¹ is a Group 15 atom; Q² is a Group 15 atom or a Group 16atom, wherein n is 0 if Q² is a Group 16 atom or n is 1 if Q² is a Group15 atom; R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl; each R² isindependently a hydrogen, a substituted or unsubstituted linear,branched, cyclic, polycyclic, or aromatic hydrocarbyl, or aheteroatom-containing group; and each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, andR¹⁰ is independently a hydrogen, a halogen, a substituted orunsubstituted linear, branched, cyclic, polycyclic, or aromatic C₁-C₄₀hydrocarbyl, or a heteroatom-containing group; or two or more adjacentR³-R¹⁰ groups are joined together to form a C₄-C₆₂ cyclic, polycyclic,heterocyclic, or aromatic group;

L¹ is

and is not part of an aromatic ring;

L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10;

each instance of R¹¹ is independently a hydrogen, a halogen, asubstituted or unsubstituted hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R¹¹ groups are joined together to form aC₄-C₆₂ cyclic, polycyclic, or heterocyclic group that is not aromatic;and each instance of R¹² is independently a hydrogen, a halogen, asubstituted or unsubstituted hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R¹² groups are joined together to form aC₄-C₆₂ cyclic, polycyclic, or heterocyclic group that is not aromatic.

21A. The ligand of paragraph 20A, wherein R¹ is a substituted orunsubstituted C₁-C₁₀ diyl; wherein L¹ is an unsubstituted methanediyland L² is an unsubstituted ethanediyl; wherein Q² is N, n is 2; each R²is independently hydrogen or unsubstituted C₁-C₁₀ hydrocarbyl; each R³,R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently hydrogen, halogen,methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclohexyl,cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl, anthracenyl,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, isomers thereof, halide substitutes thereof, or othersubstitutes thereof.22A. The ligand of paragraph 20A, wherein R¹ is selected fromunsubstituted methanediyl, ethanediyl, propanediyl, butanediyl, orpentanediyl; L¹ is an unsubstituted methanediyl and L² is anunsubstituted ethanediyl; Q² is N, n is 2, each R² is independentlymethyl or ethyl; each of R⁶ and R¹⁰ is independently halogen, phenyl,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof.23A. The ligand of paragraph 20A, wherein R⁶ is carbazolyl or fluorenyland R¹⁰ is halogen, phenyl, carbazolyl, or fluorenyl; R⁴ and R⁸ isindependently substituted or unsubstituted linear or branched C₁-C₄hydrocarbyl; and Q¹ and Q² are N.

EXPERIMENTAL

All air sensitive syntheses are carried out in nitrogen or argon purgeddry boxes. All solvents are available from commercial sources.Paraformaldehyde, 2-carbazolyl-4-methylphenol, N,N-dimethylformamide(DMF), triethylamine, N,N-dimethylethylenediamine, sodiumcyanoborohydride, acetic acid, 2-bromo-4-methylphenol, allyl bromide,potassium carbonate, methoxymethyl chloride (MOM-Cl), ozone, toluene,tetrabenzyl hafnium, tetrabenzyl zirconium, and other precursors,reagents, and solvents are available from commercial sources.

¹H NMR for Ligand and Catalyst Characterization:

Chemical structures are determined by ¹H NMR. ¹H NMR data are collectedat room temperature (e.g., 23° C.) in a 5 mm probe using either a 400 or500 MHz Bruker spectrometer with deuterated methylene chloride ordeuterated benzene.

EXAMPLES

3-(9H-carbazol-9-yl)-2-hydroxy-5-methylbenzaldehyde (B)

2-(carbazolyl)-4-methylphenol (9.65 mmol), magnesium dichloride (2.5equiv.), trimethylamine (3.0 equiv.), and paraformaldehyde (6 equiv.)were slurried in 150 mL of acetonitrile. The slurry was stirred at RTfor 2 hours during which the slurry changed to bright yellow in color.The reaction flask was then cooled to −35° C. and DMF (5 equiv.) wasslowly added. The reaction was allowed to warm to RT and stir overnight.It was poured into 250 mL of 1M HCl and extracted with ethyl acetate.The organic layer was washed with brine, collected, dried with MgSO₄,and filtered. Solvent was removed. The residue was purified on a silicaBiotage SNAP Ultra column with a gradient of 0-20% ethyl acetate/hexane.

2-(9H-carbazol-9-yl)-6-(((2-(dimethylamino)ethyl)amino)methyl)-4-methylphenol(C)

A 100 mL round-bottom flask was charged with the above aldehyde (B) (2.0equiv.), N1,N1-dimethylethane-1,2-diamine (5.0 equiv.), and 40 mL ofmethanol. To the stirred mixture was added sodium cyanoborohydride andacetic acid at room temperature. After stirring overnight, volatileswere removed and the residue redissolved in 50 mL of dichloromethane.The mixture was washed with water (2×50 mL), and the organic portiondried with MgSO₄, and filtered to remove salts. The solvent was reducedand the remainder placed onto a Biotage samplet cartridge. A solventgradient of 5-20% ethyl acetate in hexane was used to purify compound C.

2-(2-((3-(9H-carbazol-9-yl)-2-hydroxy-5-methylbenzyl)(2-(dimethylamino)ethyl)amino)ethyl)-6-bromo-4-methylphenol (E)

The amine C (1 equiv.) and2-(3-bromo-2-(methoxymethoxy)-5-methylphenyl)acetaldehyde (1 equiv.)were dissolve in methanol in a 100 mL round-bottom flask. Sodiumcyanoborohydride and acetic acid were added the mixture stirred at roomtemperature overnight. Volatiles were removed and the residueredissolved in 50 mL of dichloromethane. The mixture was washed withwater (2×50 mL), and the organic portion dried with MgSO₄, and filteredto remove salts. The solvent was reduced and the remainder placed onto aBiotage samplet cartridge. A solvent gradient of 5-20% ethyl acetate inhexane was used to purify the protected ligand. In a 50 mL round-bottomflask, the compound was dissolved in 20 mL of tetrahydrofuran.Hydrochloric acid (10 equiv.) in THF was added and the reaction stirredovernight. Solid sodium bicarbonate was added to basify the solution,which was then extracted with ethyl acetate (30 mL). The organic portionwas washed with water (2×30 mL), dried with MgSO₄, filtered, and thesolvent removed. The residue was purified using a Biotage Ultra silicacolumn with a solvent gradient of 5-40% ethyl acetate in hexane.

Metallation: In a nitrogen atmosphere, the ligand E was dissolved in 4mL of toluene in a 20 mL vial. Tetrabenzyl zirconium or hafnium wasdissolved in 4 mL of toluene in a separate vial. The solutions werecombined and after 1 hour, filtered through a 0.2 μm syringe filter, thetoluene was removed, and the residue slurried in pentane. The solidswere collected and dried under vacuum. (M=Zr or Hf).

Polymerization Examples

General polymerization procedures for parallel pressure reactor.Solvents, polymerization-grade toluene, and isohexane were supplied byExxonMobil Chemical Company and purified by passing through a series ofcolumns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland,Calif.), followed by two 500 cc columns in series packed with dried 3 Åmole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cccolumns in series packed with dried 5 Å mole sieves (8-12 mesh; AldrichChemical Company).

1-octene (C₈) (98%, Aldrich Chemical Company) was dried by stirring overNaK overnight followed by filtration through basic alumina (AldrichChemical Company, Brockman Basic 1).

Polymerization-grade ethylene (C₂) was used and further purified bypassing the gas through a series of columns: 500 cm³ Oxyclear cylinderfrom Labclear (Oakland, Calif.) followed by a 500 cm³ column packed withdried 3 Å mole sieves (8-12 mesh; Aldrich Chemical Company) and a 500cm³ column packed with dried 5 Å mole sieves (8-12 mesh; AldrichChemical Company).

Solutions of the metal complexes and activators were prepared in adrybox using toluene (ExxonMobil Chemical Company; anhydrous, storedunder nitrogen; 98%). Concentrations were 0.2 mmol/L for the metalcomplexes and N,N-dimethyl anilinium tetrakis-pentafluorophenyl borate(DMAH-PFPB) and 0.5% w/w for methyl alumoxane (MAO).

Slurries of supported catalysts in toluene were prepared in the dryboxusing 45 mg of the supported catalyst and 15 mL of toluene. Theresulting mixture was vortexed for uniform distribution of particlesprior to injection.

For polymerization experiments with supported catalysts or DMAH-PFPB asactivator, tri-n-octylaluminum (TNOAL, neat, AkzoNobel) was used as ascavenger. Concentration of the TNOAL solution in toluene ranged from0.5 to 2 mmol/L.

Polymerizations were carried out in a parallel, pressure reactor, asgenerally described in U.S. Pat. Nos. 6,306,658; 6,455,316; 6,489,168;WO 2000/009255; and Murphy et al. (2003) J. Am. Chem. Soc., v. 125, pp.4306-4317, each of which is fully incorporated herein by reference. Theexperiments were conducted in an inert atmosphere (N2) drybox usingautoclaves equipped with an external heater for temperature control,glass inserts (internal volume of reactor=23.5 mL for C2 and C2/C8; 22.5mL for C₃ runs), septum inlets, regulated supply of nitrogen, ethyleneand propylene, and equipped with disposable PEEK mechanical stirrers(800 RPM). The autoclaves were prepared by purging with dry nitrogen at110° C. or 115° C. for 5 hours and then at 25° C. for 5 hours.

Catalyst systems dissolved in solution were used in the polymerizationexamples below, unless specified otherwise.

Ethylene-Octene Copolymerization (EO)(see Tables 1 and 2).

A pre-weighed glass vial insert and disposable stirring paddle werefitted to each reaction vessel of the reactor, which contains 48individual reaction vessels. The reactor was then closed and purged withethylene. Each vessel was charged with enough solvent (such asisohexane) to bring the total reaction volume, including the subsequentadditions, to the desired volume, such as 5 mL. 1-octene, if required,was injected into the reaction vessel and the reactor was heated to theset temperature and pressurized to the predetermined pressure ofethylene, while stirring at 800 rpm. The aluminum and/or zinc compoundin toluene was then injected as scavenger and/or chain transfer agentfollowed by addition of the activator solution (such as 1-1.2 molarequivalents of N,N-dimethyl anilinium tetrakis-pentafluorophenylborate-DMAH-PFPB).

The catalyst solution (such as 0.020-0.080 μmol of metal complex) wasinjected into the reaction vessel and the polymerization was allowed toproceed until a pre-determined amount of ethylene (quench value 20 psi)had been used up by the reaction. Alternatively, the reaction may beallowed to proceed for a set amount of time (for example, maximumreaction time 30 minutes). Ethylene was added continuously (through theuse of computer controlled solenoid valves) to the autoclaves duringpolymerization to maintain reactor gauge pressure (+/−2 psig) and thereactor temperature was monitored and maintained within +/−1° C. Thereaction was quenched by pressurizing the vessel with compressed air.After the reactor was vented and cooled, the glass vial insertcontaining the 30 polymer product and solvent was removed from thepressure cell and the inert atmosphere glove box, and the volatilecomponents were removed using a Genevac HT-12 centrifuge and GenevacVC3000D vacuum evaporator operating at elevated temperature and reducedpressure. The vial was then weighed to determine the yield of thepolymer product. The resultant polymer was analyzed by Rapid GPC (seebelow) to determine the molecular weight, by FT-IR (see below) todetermine percent octene incorporation, and by DSC (see below) todetermine melting point (Tm).

For polymerizations using MAO as activator (such as 100 to 1,000 molarequivalents), the MAO solution was injected into the reaction vesselafter the addition of 1- octene and prior to heating the vessel to theset temperature and pressurizing with ethylene. No additional aluminumreagent was used as scavenger during these runs.

Equivalence is determined based on the mole equivalents relative to themoles of the transition metal in the catalyst complex.

For polymerizations using MAO as activator, the MAO solution wasinjected into the vessel after the addition of isohexane. No additionalaluminum reagent was used as scavenger during these runs.

Polymerizations using Catalysts (Tables 1 and 2). For ethylene-octenecopolymerization (EO), the reactor was prepared as described above andpurged with ethylene. Isohexane, 1-octene (100 μL), and the scavengersolution were added sequentially to the reaction vessel via syringe atroom temperature and atmospheric pressure. If the reactor was heated tothe process temperature of 80° C., it was then charged with ethylene tothe pressure setpoint of 95 psig (95 psig=655 kPa) while stirring at 800rpm. If the reactor was then heated to the process temperature of 100°C., it was then charged with ethylene to the pressure setpoint of 135psig (135 psig=931 kPa) while stirring at 800 rpm. The supportedcatalyst slurry was injected into the vessel and the polymerization wasallowed to proceed as described in the previous section. To test forcatalyst response to hydrogen, the EO experiments were also carried outusing 300 ppm H₂/5 ethylene mixed gas.

Polymer Characterization. Polymer sample solutions were prepared bydissolving polymer in 1,2,4-trichlorobenzene (TCB, 99+% purity fromSigma-Aldrich) containing 2,6-di-tertbutyl-4-methylphenol (BHT, 99% fromAldrich) at 165° C. in a shaker oven for approximately 3 hours. Theconcentration of polymer in solution was between 0.1 mg/mL to 0.9 mg/mLwith a BHT concentration of 1.25 mg BHT/mL of TCB.

Gel Permeation Chromatography-Tosoh EcoSEC High Temperature GPC System(GPC-Tosoh EcoSEC)—

Mw, Mn and Mw/Mn were determined by using a High Temperature GelPermeation Chromatography (Tosoh Bioscience, LLC), equipped with adifferential refractive index detector (DRI). Three high temperature TSKgel column (Tosoh GMHHR-H(30)HT2) were used. The nominal flow rate was 1mL/min, and the nominal injection volume was 300 pt. The varioustransfer lines, columns, and dual flow differential refractometer (theDRI detector) were contained in an oven maintained at 160° C. Solventfor the experiment was prepared by dissolving 1.2 grams of butylatedhydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2, 4 trichlorobenzene (TCB). The TCB mixture was then filtered through a0.1 μm Teflon filter. The TCB was then degassed with an online degasserbefore entering the GPC instrument. Polymer solutions were prepared byplacing dry polymer in glass vials, adding the desired amount of TCB,then heating the mixture at 160° C. with continuous shaking for about 2hours. All quantities were measured gravimetrically. The injectionconcentration was from 0.5 to 2 mg/mL, with lower concentrations beingused for higher molecular weight samples. Flow rate in the apparatus wasthen increased to 1 mL/minute, and the DRI was allowed to stabilize for2 hours before injecting the first sample. The molecular weight wasdetermined by combining universal calibration relationship with thecolumn calibration which was performed with a series of monodispersedpolystyrene (PS) standards. The MW was calculated at each elution volumewith the following equation:

${\log \; M_{X}} = {\frac{\log \left( {K_{X}/K_{PS}} \right)}{a_{x} + 1} + {\frac{a_{PS} + 1}{a_{X} + 1}\log \; M_{PS}}}$

where the variables with subscript “X” stand for the test sample whilethose with subscript “PS” stand for PS. In this method, a_(PS)=0.67 andK_(PS)=0.000175 while a_(X) and K_(X) are obtained from publishedliterature. Specifically, a/K=0.695/0.000579 for polyethylene and0.705/0.0002288 for polypropylene.

The concentration, c, at each point in the chromatogram was calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the refractive index increment for the system. Specifically,dn/dc=0.109 for both polyethylene and polypropylene.

The mass recovery was calculated from the ratio of the integrated areaof the concentration chromatography over elution volume and theinjection mass which was equal to the pre-determined concentrationmultiplied by injection loop volume.

All molecular weights are reported in g/mol unless otherwise noted.

Differential Scanning calorimetry (DSC) measurements were performed on aTAQ100 instrument to determine the melting point (Tm) of the polymers.Samples were preannealed at 220° C. for 15 minutes and then allowed tocool to room temperature overnight. The samples were then heated to 220°C. at a rate of 100° C./min and then cooled at a rate of 50° C./min.Melting points were collected during the heating period.

The weight percent of ethylene incorporated in polymers was determinedby rapid FTIR spectroscopy on a Bruker Equinox 55+IR in reflection mode.Samples were prepared in a thin film format by evaporative depositiontechniques. FT-IR methods were calibrated using a set of samples with arange of known wt % ethylene content. For ethylene-1-octene copolymers,the wt % octene in the copolymer was determined via measurement of themethyl deformation band at about 1,375 cm⁻¹. The peak height of thisband was normalized by the combination and overtone band at ˜4321 cm-1,which corrects for path length differences.

For ethylene-octene copolymers, the wt % ethylene is determined viameasurement of the methylene rocking band (about 770 cm⁻¹ to about 700cm⁻¹). The peak area of this band is normalized by sum of the band areasof the combination and overtone bands in the range of about 4,500 cm⁻¹to about 4000 cm⁻¹. For samples with composition outside the calibrationrange, the wt % ethylene was determined by ¹H NMR spectroscopy orestimated from the polymer Tm.

¹H NMR data were collected at 120° C. in a 5 mm probe using aspectrometer with a ¹H frequency of 500 MHz. Data was recorded using amaximum pulse width of 45°, 5 seconds between pulses and signalaveraging 120 transients. Spectral signals were integrated.

Table 1 provides the reaction conditions for ethylene octenecopolymerization (EO) using DMAH-PFPB or MAO.

TABLE 1 Catalyst loading 0.020-0.080 μmol DMAH-PFPB 1.1 equiv MAO 500equiv Temperature 80° C. or 100° C. Pressure Setpoint 95 psi or 135 psi1-octene 100 μL Solvent Isohexane Total Volume 5 mL Aluminum compound(scavenger) 0.5 μmol tri-n-octyl aluminum (TNOAL)

Tables 2 and 3 provide catalyst activity and polymer properties forethylene-octene copolymerization (EO) using DMAH-PFPB or MAO.Experiments 1-20 utilized the catalyst represented by Formula (VII)containing zirconium (Zr-VII catalyst) and Experiments 21-39 utilizedthe catalyst represented by Formula (VII) containing hafnium (Hf-VIIcatalyst). Experiments 1-10 and 21-29 included the scavenger TNOAL at aconcentration of 0.5 μmol, while the remainder of the experiments didnot contain a scavenger. The catalytic activities shown in Experiments1-20 (Zr-VII catalyst) were in a range from about 25 kg/mmol/hr to 165kg/mmol/hr. The catalytic activities shown in Experiments 21-39 (Hf-VIIcatalyst) were in a range from about 104 kg/mmol/hr to 260 kg/mmol/hr.For comparing the overall catalytic activity, the Hf-VII catalystoutperformed the Zr-VII catalyst.

Both the Zr-VII catalyst and the Hf-VII catalyst provide particularlyhigh molecular weight polymers (289 Kg/mol to 657 Kg/mol with Zr-VII;168 Kg/mol to 342 Kg/mol with Hf-VII) with narrow PDI (1.4 to 2.4) andhigh comonomer content (12.9 wt % to 19.5 wt %). For example, as shownin Tables 2 and 3, Example 11, the polymer obtained using Zr-VII as thecatalyst in presence of MAO at 80° C. and 95 psi has a comonomer content(C₈ wt %) of 19.5 wt %.

The results obtained using the novel catalysts provide promisingadvantages for processability of the polymer itself and the polymer in acomposition.

TABLE 2 Catalyst Formula Catalyst Scavenger T P Setpoint rxn timeExample (VII) Zr, Hf (μmol) Activator Scavenger (μmol) (° C.) (psi) (s)1 Zr 0.02 DMAH-PFPB TNOAL 0.5 80 95 101 2 Zr 0.02 DMAH-PFPB TNOAL 0.5 8095 94 3 Zr 0.02 DMAH-PFPB TNOAL 0.5 80 95 82 4 Zr 0.02 DMAH-PFPB TNOAL0.5 80 95 260 5 Zr 0.02 DMAH-PFPB TNOAL 0.5 80 95 112 6 Zr 0.02DMAH-PFPB TNOAL 0.5 100 135 182 7 Zr 0.02 DMAH-PFPB TNOAL 0.5 100 135371 8 Zr 0.02 DMAH-PFPB TNOAL 0.5 100 135 120 9 Zr 0.04 DMAH-PFPB TNOAL0.5 100 135 55 10 Zr 0.04 DMAH-PFPB TNOAL 0.5 100 135 52 11 Zr 0.02 MAO80 95 76 12 Zr 0.02 MAO 80 95 83 13 Zr 0.02 MAO 80 95 80 14 Zr 0.02 MAO80 95 91 15 Zr 0.02 MAO 80 95 87 16 Zr 0.02 MAO 100 135 93 17 Zr 0.02MAO 100 135 111 18 Zr 0.02 MAO 100 135 90 19 Zr 0.02 MAO 100 135 100 20Zr 0.02 MAO 100 135 105 21 Hf 0.02 DMAH-PFPB TNOAL 0.5 80 95 92 22 Hf0.02 DMAH-PFPB TNOAL 0.5 80 95 77 23 Hf 0.02 DMAH-PFPB TNOAL 0.5 80 9590 24 Hf 0.02 DMAH-PFPB TNOAL 0.5 80 95 72 25 Hf 0.02 DMAH-PFPB TNOAL0.5 80 95 73 26 Hf 0.08 DMAH-PFPB TNOAL 0.5 100 135 22 27 Hf 0.08DMAH-PFPB TNOAL 0.5 100 135 21 28 Hf 0.04 DMAH-PFPB TNOAL 0.5 100 135 3129 Hf 0.04 DMAH-PFPB TNOAL 0.5 100 135 30 30 Hf 0.02 MAO 80 95 62 31 Hf0.02 MAO 80 95 57 32 Hf 0.02 MAO 80 95 63 33 Hf 0.02 MAO 80 95 67 34 Hf0.02 MAO 80 95 62 35 Hf 0.02 MAO 100 135 55 36 Hf 0.02 MAO 100 135 64 37Hf 0.02 MAO 100 135 58 38 Hf 0.02 MAO 100 135 57 39 Hf 0.02 MAO 100 13564

TABLE 3 Catalyst Formula yield activity Mw Mn wt % Tm Example (VII) Zr,Hf (g) (kg/mmol/hr) (kg/mol) (kg/mol) Mw/Mn C8= (° C.) 1 Zr 0.056 100366 209 1.8 17.8 88.1 2 Zr 0.053 101 381 225 1.7 17.9 88.8 3 Zr 0.055121 337 206 1.6 16.7 91.4 4 Zr 0.044 30 445 263 1.7 17.5 92.2 5 Zr 0.05385 406 212 1.9 17.1 86.6 6 Zr 0.051 51 347 181 1.9 15.8 95.3 7 Zr 0.05125 328 190 1.7 16.3 96.0 8 Zr 0.049 74 337 209 1.6 15.5 96.7 9 Zr 0.067111 348 202 1.7 15.2 95.1 10 Zr 0.067 115 316 170 1.9 12.9 95.7 11 Zr0.070 165 289 176 1.6 19.5 86.8 12 Zr 0.072 155 327 190 1.7 17.2 88.1 13Zr 0.073 165 369 215 1.7 17.8 87.8 14 Zr 0.062 122 314 185 1.7 17.3 87.015 Zr 0.059 122 351 195 1.8 18.3 85.3 16 Zr 0.041 80 577 348 1.7 16.093.4 17 Zr 0.056 91 589 364 1.6 16.8 89.6 18 Zr 0.055 110 645 393 1.614.1 94.1 19 Zr 0.053 95 657 458 1.4 16.3 91.6 20 Zr 0.052 89 647 4301.5 15.9 90.6 21 Hf 0.053 104 302 180 1.7 17.7 92.0 22 Hf 0.060 140 258143 1.8 18.6 90.4 23 Hf 0.054 108 270 165 1.6 16.5 94.5 24 Hf 0.064 161327 185 1.8 17.8 90.3 25 Hf 0.063 155 334 199 1.7 16.9 92.3 26 Hf 0.105212 202 89 2.3 14.4 101.1 27 Hf 0.095 207 184 76 2.4 14.6 102.1 28 Hf0.083 242 236 103 2.3 14.8 97.6 29 Hf 0.076 230 180 101 1.8 17.0 98.5 30Hf 0.089 260 169 83 2.0 17.2 91.055 31 Hf 0.078 247 186 104 1.8 18.987.91 32 Hf 0.079 226 191 109 1.8 18.4 89.091 33 Hf 0.068 183 168 92 1.819.5 86.9 34 Hf 0.071 205 230 134 1.7 18.8 86.3 35 Hf 0.067 218 268 1671.6 16.7 93.6 36 Hf 0.065 184 288 176 1.6 15.9 94.2 37 Hf 0.064 199 280147 1.9 16.7 93.1 38 Hf 0.061 191 302 182 1.7 17.1 91.5 39 Hf 0.060 168342 194 1.8 16.7 95.7

Overall, the present disclosure provides catalyst compounds including anonsymmetric bridged amine bis(phenolate), catalyst systems includingsuch, and uses thereof. Catalyst compounds, catalyst systems, andprocesses of the present disclosure can provide high comonomer contentand high molecular weight polymers having narrow PDI values,contributing to good processability for the polymer itself and for thepolymer used in a composition.

The phrases, unless otherwise specified, “consists essentially of” and“consisting essentially of” do not exclude the presence of other steps,elements, or materials, whether or not, specifically mentioned in thisspecification, so long as such steps, elements, or materials, do notaffect the basic and novel characteristics of the present disclosure,additionally, they do not exclude impurities and variances normallyassociated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures to the extentthey are not inconsistent with this text. As is apparent from theforegoing general description and the specific embodiments, while formsof the present disclosure have been illustrated and described, variousmodifications can be made without departing from the spirit and scope ofthe present disclosure. Accordingly, it is not intended that the presentdisclosure be limited thereby. Likewise, the term “comprising” isconsidered synonymous with the term “including.” Likewise whenever acomposition, an element or a group of elements is preceded with thetransitional phrase “comprising,” it is understood that we alsocontemplate the same composition or group of elements with transitionalphrases “consisting essentially of,” “consisting of,” “selected from thegroup of consisting of,” or “is” preceding the recitation of thecomposition, element, or elements and vice versa.

While the present disclosure has been described with respect to a numberof embodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the present disclosure.

What is claimed is:
 1. A catalyst compound represented by Formula (II):

wherein: M is a Group 4 transition metal; each X¹ and X² isindependently a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic hydrocarbyl; or X¹ and X² are joined together toform a C₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group; Q¹ isa Group 15 atom; Q² is a Group 15 atom or a Group 16 atom, wherein n is0 if Q² is a Group 16 atom or n is 1 if Q² is a Group 15 atom; R¹ is asubstituted or unsubstituted linear, branched, cyclic, polycyclic,heterocyclic, or aromatic C₁-C₁₈ diyl; each R² is independently ahydrogen, a substituted or unsubstituted linear, branched, cyclic,polycyclic, or aromatic hydrocarbyl, or a heteroatom-containing group;and each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independently ahydrogen, a halogen, a substituted or unsubstituted linear, branched,cyclic, polycyclic, or aromatic hydrocarbyl, or a heteroatom-containinggroup; or two or more adjacent R³-R¹⁰ groups are joined together to forma C₄-C₆₂ cyclic, polycyclic, heterocyclic, or aromatic group; L¹ is

and is not part of an aromatic ring; L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10; each instance of R¹¹ is independently a hydrogen,a halogen, a substituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and each instance of R¹² is independently ahydrogen, a halogen, a substituted or unsubstituted C₁-C₄₀ hydrocarbyl,or a heteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.
 2. The catalyst compound of claim 1, whereinM is Hf or Zr.
 3. The catalyst compound of claim 1, wherein each X¹ andX² is independently a substituted or unsubstituted C₁-C₈ alkyl, phenyl,benzyl, naphthyl, or cyclohexyl.
 4. The catalyst compound of claim 1,wherein R¹ is a substituted or unsubstituted C₁-C₁₀ diyl.
 5. Thecatalyst compound of claim 1, wherein R¹ is selected from methanediyl,ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl,heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl,dodecanediyl, isomers thereof, halide substitutes thereof, or othersubstitutes thereof.
 6. The catalyst compound of claim 1, wherein R¹ isselected from unsubstituted methanediyl, ethanediyl, propanediyl,butanediyl, or pentanediyl.
 7. The catalyst compound of claim 1, whereinL¹ is an unsubstituted methanediyl and L² is an unsubstitutedethanediyl.
 8. The catalyst compound of claim 1, wherein Q² is N, n is2, and each R² is independently hydrogen or unsubstituted C₁-C₁₀hydrocarbyl.
 9. The catalyst compound of claim 1, wherein Q² is N, n is2, and each R² is independently methyl or ethyl.
 10. The catalystcompound of claim 1, wherein each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ isindependently hydrogen, halogen, methyl, ethyl, ethenyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl,anthracenyl, carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl,imidazolyl, indenyl, indanyl, isomers thereof, halide substitutesthereof, or other substitutes thereof.
 11. The catalyst compound ofclaim 10, wherein each of R⁶ and R¹⁰ is independently halogen, phenyl,carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl, imidazolyl,indenyl, indanyl, or substitutes thereof.
 12. The catalyst compound ofclaim 11, wherein R⁶ is carbazolyl or fluorenyl and R¹⁰ is halogen,phenyl, carbazolyl, or fluorenyl.
 13. The catalyst compound of claim 1,wherein R⁴ and R⁸ is independently substituted or unsubstituted linearor branched C₁-C₄ hydrocarbyl.
 14. The catalyst compound of claim 1,wherein Q¹ and Q² are N.
 15. The catalyst compound of claim 1, wherein Mis Hf or Zr; X¹ and X² is independently a substituted or unsubstitutedC₁-C₈ alkyl, phenyl, benzyl, naphthyl, or cyclohexyl, and R¹ is asubstituted or unsubstituted C₁-C₁₀ diyl.
 16. The catalyst compound ofclaim 1, wherein M is Hf or Zr; X¹ and X² is independently a substitutedor unsubstituted C₁-C₈ alkyl, phenyl, benzyl, naphthyl, or cyclohexyl,and R¹ is selected from methanediyl, ethanediyl, propanediyl,butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl,nonanediyl, decanediyl, undecanediyl, dodecanediyl, isomers thereof,halide substitutes thereof, or other substitutes thereof.
 17. Thecatalyst compound of claim 1, wherein R¹ is selected from unsubstitutedmethanediyl, ethanediyl, propanediyl, butanediyl, or pentanediyl, and L¹is an unsubstituted methanediyl and L² is an unsubstituted ethanediyl.18. The catalyst compound of claim 1, wherein M is Hf or Zr; X¹ and X²is independently a substituted or unsubstituted C₁-C₈ alkyl, phenyl,benzyl, naphthyl, or cyclohexyl; R¹ is selected from methanediyl,ethanediyl, propanediyl, butanediyl, pentanediyl, hexanediyl,heptanediyl, octanediyl, nonanediyl, decanediyl, undecanediyl,dodecanediyl, isomers thereof, halide substitutes thereof, or othersubstitutes thereof; each R² is independently hydrogen or unsubstitutedC₁-C₁₀ hydrocarbyl; R⁶ is carbazolyl or fluorenyl; R¹⁰ is halogen,phenyl, carbazolyl, or fluorenyl; R⁴ and R⁸ is independently substitutedor unsubstituted linear or branched C₁-C₄ hydrocarbyl; and Q¹ and Q² areN.
 19. The catalyst compound of claim 1, wherein the catalyst compoundis selected from:


20. The catalyst compound of claim 1 wherein the catalyst compound isselected from:


21. A catalyst system comprising an activator and the catalyst compoundof claim
 1. 22. The catalyst system of claim 21, further comprising asupport material.
 23. The catalyst system of claim 21, furthercomprising a support material, wherein the support material is selectedfrom Al₂O₃, ZrO₂, SiO₂, SiO₂/Al₂O₃, SiO₂/TiO₂, silica clay, siliconoxide/clay, or mixtures thereof.
 24. The catalyst system of claim 21,wherein the activator comprises an alkylalumoxane or an non-coordinatinganion.
 25. A process for the production of an ethylene alpha-olefincopolymer comprising: polymerizing ethylene and at least one C₃-C₂₀alpha-olefin by contacting the ethylene and the at least one C₃-C₂₀alpha-olefin with a catalyst system of claim 21 in at least one solutionpolymerization reactor at a reactor pressure of from 2 MPa to 200 MPaand a reactor temperature of from 10° C. to 250° C. to form an ethylenealpha-olefin copolymer.
 26. The process of claim 25, wherein thecatalyst has an activity of 100,000 g/mmol/hr or greater.
 27. Theprocess of claim 25, wherein the ethylene alpha-olefin copolymer has anMw value of from 250,000 to 700,000 g/mol.
 28. The process of claim 25,wherein the ethylene alpha-olefin copolymer has an Mw/Mn value of 5 orless.
 29. The process of claim 25, wherein the ethylene alpha-olefincopolymer has an Mw/Mn value of from 1 to
 2. 30. A catalyst systemcomprising an activator and the catalyst compound of claim
 20. 31. Aprocess for the production of an ethylene alpha-olefin copolymercomprising: polymerizing ethylene and at least one C₃-C₂₀ alpha-olefinby contacting the ethylene and the at least one C₃-C₂₀ alpha-olefin witha catalyst system of claim 30 in at least one solution polymerizationreactor at a reactor pressure of from 2 MPa to 200 MPa and a reactortemperature of from 10° C. to 250° C. to form an ethylene alpha-olefincopolymer.
 32. The process of claim 25, wherein the ethylenealpha-olefin copolymer has a comonomer content of 12 wt % or greater.33. The process of claim 31, wherein the ethylene alpha-olefin copolymerhas a comonomer content of 15 wt % or greater.
 34. The process of claim25, wherein the ethylene alpha-olefin copolymer has a comonomer contentof 17 wt % or greater.
 35. An ethylene alpha-olefin copolymer comprisingethylene and at least one C₃-C₂₀ alpha-olefin, wherein the copolymer hasan Mw value of from 250,000 to 700,000 g/mol, an Mw/Mn value of 5 orless, and a comonomer content of 12 wt % or greater.
 36. The copolymerof claim 35, wherein the alpha-olefin is octene, has an Mw/Mn value offrom 1 to 2, and the copolymer has a comonomer content of 15 wt % orgreater.
 37. A ligand represented by Formula (I):

wherein: Q¹ is a Group 15 atom; Q² is a Group 15 atom or a Group 16atom, wherein n is 0 if Q² is a Group 16 atom or n is 1 if Q² is a Group15 atom; R¹ is a substituted or unsubstituted linear, branched, cyclic,polycyclic, heterocyclic, or aromatic C₁-C₁₈ diyl; each R² isindependently a hydrogen, a substituted or unsubstituted linear,branched, cyclic, polycyclic, or aromatic C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; and each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, andR¹⁰ is independently a hydrogen, a halogen, a substituted orunsubstituted linear, branched, cyclic, polycyclic, or aromatic C₁-C₄₀hydrocarbyl, or a heteroatom-containing group; or two or more adjacentR³-R¹⁰ groups are joined together to form a C₄-C₆₂ cyclic, polycyclic,heterocyclic, or aromatic group; L¹ is

and is not part of an aromatic ring; L² is

and is not part of an aromatic ring, wherein y is an integer of 2, 3, 4,5, 6, 7, 8, 9, or 10; each instance of R¹¹ is independently a hydrogen,a halogen, a substituted or unsubstituted C₁-C₄₀ hydrocarbyl, or aheteroatom-containing group; or two or more adjacent R¹¹ groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic; and each instance of R¹² is independently ahydrogen, a halogen, a substituted or unsubstituted C₁-C₄₀ hydrocarbyl,or a heteroatom-containing group; or two or more adjacent R¹² groups arejoined together to form a C₄-C₆₂ cyclic, polycyclic, or heterocyclicgroup that is not aromatic.
 38. The ligand of claim 37, wherein R¹ is asubstituted or unsubstituted C₁-C₁₀ diyl; wherein L¹ is an unsubstitutedmethanediyl and L² is an unsubstituted ethanediyl; wherein Q² is N, n is2; each R² is independently hydrogen or unsubstituted C₁-C₁₀hydrocarbyl; each R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, and R¹⁰ is independentlyhydrogen, halogen, methyl, ethyl, ethenyl, propyl, butyl, pentyl, hexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,cyclohexyl, cyclooctyl, phenyl, benzyl, naphthyl, phenanthryl,anthracenyl, carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl,imidazolyl, indenyl, indanyl, isomers thereof, halide substitutesthereof, or other substitutes thereof.
 39. The ligand of claim 37,wherein R¹ is selected from unsubstituted methanediyl, ethanediyl,propanediyl, butanediyl, or pentanediyl; L¹ is an unsubstitutedmethanediyl and L² is an unsubstituted ethanediyl; Q² is N, n is 2, eachR² is independently methyl or ethyl; each of R⁶ and R¹⁰ is independentlyhalogen, phenyl, carbazolyl, fluorenyl, adamantyl, indolyl, indolinyl,imidazolyl, indenyl, indanyl, or substitutes thereof.
 40. The ligand ofclaim 37, wherein R⁶ is carbazolyl or fluorenyl and R¹⁰ is halogen,phenyl, carbazolyl, or fluorenyl; R⁴ and R⁸ is independently substitutedor unsubstituted linear or branched C₁-C₄ hydrocarbyl; and Q¹ and Q² areN.
 41. The ligand of claim 37, wherein the ligand is selected from:


42. The catalyst compound of claim 1, wherein L¹ is a substituted orunsubstituted methanediyl and L² is a substituted or unsubstitutedethanediyl.
 43. The catalyst system of claim 21, wherein L¹ is asubstituted or unsubstituted methanediyl and L² is a substituted orunsubstituted ethanediyl.